WO2018190405A1 - FeNi ORDERED ALLOY, FeNi ORDERED ALLOY MAGNET, AND METHOD FOR MANUFACTURING FeNi ORDERED ALLOY - Google Patents

FeNi ORDERED ALLOY, FeNi ORDERED ALLOY MAGNET, AND METHOD FOR MANUFACTURING FeNi ORDERED ALLOY Download PDF

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WO2018190405A1
WO2018190405A1 PCT/JP2018/015436 JP2018015436W WO2018190405A1 WO 2018190405 A1 WO2018190405 A1 WO 2018190405A1 JP 2018015436 W JP2018015436 W JP 2018015436W WO 2018190405 A1 WO2018190405 A1 WO 2018190405A1
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feni
alloy
ordered alloy
feni ordered
treatment
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PCT/JP2018/015436
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French (fr)
Japanese (ja)
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翔 後藤
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株式会社デンソー
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Priority to DE112018002014.2T priority Critical patent/DE112018002014T5/en
Priority to CN201880024767.4A priority patent/CN110506313B/en
Publication of WO2018190405A1 publication Critical patent/WO2018190405A1/en
Priority to US16/574,514 priority patent/US11427895B2/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02—Extraction of non-metals
    • C21D3/08—Extraction of nitrogen
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/068—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder having a L10 crystallographic structure, e.g. [Co,Fe][Pt,Pd] (nano)particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • L1 0 type FeNi ordered alloy having an L1 0 type ordered structure
  • FeNi ordered alloy magnet which is constructed by using such a L1 0 type FeNi ordered alloy
  • L1 0 type (Eruwanzero type) of FeNi (iron - nickel) ordered alloy is expected as a magnet material and magnetic recording material uses no rare earth and precious metals.
  • the L1 0 type ordered structure is a crystal structure in which Fe and Ni are arranged in layers in the (001) direction based on a face-centered cubic lattice.
  • Such L1 0 ordered structure is, FePt, FePd, seen in alloys such AuCu, usually, a disordered alloy rules - heat treatment at below disorder transition temperature t [lambda, obtained by prompting diffusion.
  • the transition temperature T ⁇ to obtain L1 0 type FeNi ordered alloy is 320 ° C. and cold, it is difficult at this temperature following synthesizing only the heat treatment for diffusion is very slow. Therefore, conventionally, various attempts to synthesize the L1 0 type FeNi ordered alloy have been made.
  • MBE molecular beam epitaxy
  • the present disclosure aims to provide an FeNi ordered alloy that can be used also as a magnet material and a magnetic recording material, and to provide an FeNi ordered alloy magnet constituted by using the FeNi ordered alloy.
  • FeNi ordered alloy of the first aspect of the present disclosure includes an L1 0 type ordered structure, the average degree of order of the overall material is 0.4 or more and a coercive force 87.5kA / m or more and Has been.
  • a FeNi ordered alloy having a degree of order of 0.4 or more and a coercive force of 87.5 kA / m or more
  • a FeNi ordered alloy that can also be used as a magnet material or a magnetic recording material is obtained.
  • an FeNi ordered alloy magnet can be obtained using such an FeNi ordered alloy.
  • a nitriding process for nitriding the FeNi disordered alloy (100) and a denitrification process for removing nitrogen from the nitridated FeNi disordered alloy are performed.
  • L1 0 type FeNi ordered alloy is 87.5kA / m or more
  • the treatment temperature is 300 ° C. or more and 500 ° C. or less, and the treatment time is 10 hours or more.
  • the method of manufacturing such a FeNi ordered alloy, the overall average degree of order of 0.4 or more materials, and the L1 0 type FeNi ordered alloy coercivity is 87.5kA / m or more, easily Can be synthesized.
  • the method comprising synthesizing the compound of Fe and Ni are aligned in the same lattice structure as the L1 0 type FeNi ordered structure, Fe and Ni from compound anda generating an L1 0 type FeNi ordered alloy by removing unnecessary elements other than, by combining the compound, the process temperature of 200 ° C. or higher 500 ° C. or less, the treatment time over 10 hours
  • FeNiN as an intermediate product is synthesized as a compound by nitriding the FeNi disordered alloy.
  • Degree of order S is a diagram showing a simulation result of X-ray diffraction pattern of the L1 0 type FeNi ordered alloy is 1. It is a figure which shows the simulation result of the X-ray diffraction pattern of a FeNi disordered alloy. It is a figure which shows the measurement result of the X-ray-diffraction pattern of the FeNi ordered alloy in comparative example S0, S2, S3. It is a figure which shows the measurement result of the X-ray-diffraction pattern of the FeNi ordered alloy in comparative example S1, S3. It is a figure which shows the measurement result of the X-ray-diffraction pattern of the FeNi ordered alloy in comparative example S3, S4, S5.
  • Degree of order S is a diagram showing an X-ray diffraction pattern of the powder of L1 0 type FeNi ordered alloy when it is 1. It is the graph which showed the relationship between the regularity S and diffraction intensity ratio. Is a graph showing measurement results of X-ray diffraction pattern of the L1 0 type FeNi ordered alloy manufactured by the manufacturing method of the second embodiment.
  • L1 0 type FeNi ordered alloy according to the present embodiment i.e. FeNi superlattice is intended to be applied to a magnetic material such as magnetic materials and magnetic recording materials, in the degree of order S is 0.4 or more, the coercive force Hc Is as large as 87.5 kA / m or more and has excellent magnetic properties.
  • the degree of order S indicates the degree of ordering in the FeNi superlattice.
  • L1 0 ordered structure is a basic structure of the face-centered cubic lattice has a lattice structure as shown in FIG.
  • the uppermost layer in the [001] plane laminated structure of the face-centered cubic lattice is the I site
  • the intermediate layer located between the uppermost layer and the lowermost layer is the II site.
  • the ratio of the presence of metal A at the I site is x and the ratio of the presence of metal B is 1-x
  • the ratio of the presence of metal A and metal B at the I site is expressed as A x B 1-x.
  • the ratio of the presence of metal B at the II site is x and the ratio of the presence of metal A is 1-x
  • the ratio of the presence of metal A and metal B at the II site is expressed as A 1-x B x.
  • x satisfies 0.5 ⁇ x ⁇ 1.
  • the white and black ones indicate that Ni is 50% and Fe is 50%.
  • the regularity S expressed in this way is, for example, biased toward Ni serving as metal A at the I site and biased toward Fe serving as metal B at the II site, and the overall average regularity S as in the present embodiment.
  • the degree of order S needs to be high on average throughout the material, and good magnetic properties cannot be obtained even if the value is locally high.
  • the regularity S needs to be equal to or higher than a predetermined value in all the lattices of the face-centered cubic lattice formed by the L1 0 type regular structure, and the regularity S is locally high in some lattices. Even if the apparent regularity S is the same, the magnetic properties are not improved. For this reason, even if it is a locally high value, the average average regularity S here is not included in 0.4 or more.
  • the coercive force Hc is obtained as the strength of the magnetic field when a magnetic field is applied to the obtained FeNi ordered alloy and the magnetization direction of the FeNi ordered alloy is switched by the influence of the magnetic field.
  • FIG. 3A it has a bottomed cylindrical container portion 1a having an inner diameter of 2 mm and a height of 7 mm, and a columnar rod-like portion 1b having an outer diameter of 2 mm and a height of 15 mm.
  • a sample holder 1 is prepared. Then, as shown in (b) of FIG. 3, while 10 mg of FeNi ordered alloy particles are filled in the container 1a, as shown in (c) of FIG. 3, from the opening side of the container 1a.
  • the FeNi ordered alloy is pressed by the rod-like portion 1 b of another sample holder 1.
  • the sample 2 whose shape is fixed in a cylindrical shape in the container portion 1a is created.
  • a sufficiently large magnetic field is applied to the FeNi ordered alloy sample 2 to bring it to a saturation state where the magnetization of the sample 2 does not increase any more.
  • a magnetic field in the opposite direction to the previous one is applied, and the timing at which the magnetization of the sample 2 becomes zero is detected.
  • the strength of the magnetic field at that time is defined as a coercive force Hc.
  • Hc coercive force
  • the FeNi ordered alloy has a degree of order S of 0.4 or more and a coercive force Hc of 87.5 kA / m or more. It was also found that the coercive force Hc of the FeNi ordered alloy depends on the grain size of the FeNi ordered alloy and the manufacturing method. In order to obtain a higher coercive force Hc, it is desirable to make the grain size and manufacturing method of the FeNi ordered alloy more suitable as described later.
  • Such L1 0 type FeNi ordered alloy for example, after the nitriding process of nitriding the FeNi disordered alloy, by performing a denitrification treatment for removing nitrogen from nitriding treated FeNi disordered alloy, obtained It is done.
  • An irregular alloy is an alloy in which the arrangement of atoms is random without regularity.
  • a powder sample of an FeNi disordered alloy produced by a thermal plasma method, a flame spray method, or a coprecipitation method is processed under the nitriding conditions and the denitrifying conditions shown in FIG. is there. Then, the alloy after these processes, subjected to X-ray diffraction measurement, is obtained by evaluating whether L1 0 ordered structure is formed.
  • the composition ratio is the atomic weight ratio of Fe: Ni, and the particle diameter is the volume average particle diameter (unit: nm). It is shown. Moreover, about the nitriding treatment condition and the denitrification treatment condition, the treatment temperature (unit: ° C.) and the treatment time (unit: h) are shown.
  • Nitriding treatment and denitrification treatment are performed using, for example, a manufacturing apparatus shown in FIG.
  • the manufacturing apparatus includes a tubular furnace 10 as a heating furnace heated by a heater 11 and a glove box 20 for installing a sample in the tubular furnace 10.
  • this manufacturing apparatus switches Ar (argon) as a purge gas, NH 3 (ammonia) for nitriding treatment, and H 2 (hydrogen) for denitrification treatment, and switches the tube.
  • Ar argon
  • NH 3 ammonia
  • H 2 hydrogen
  • the manufacturing method of this embodiment using such a manufacturing apparatus is as follows. First, a powder sample of the FeNi disordered alloy 100 is placed in the tubular furnace 10. In the nitriding treatment, NH 3 gas is introduced into the tubular furnace 10 to make the inside of the tubular furnace 10 an NH 3 atmosphere, and the FeNi disordered alloy is heated and nitrided at a predetermined temperature for a predetermined time.
  • H 2 gas is introduced into the heating furnace to make the inside of the tubular furnace 10 into an H 2 atmosphere, and the FeNi disordered alloy that has been nitrided at a predetermined temperature for a predetermined time is heated to remove nitrogen.
  • Hc in average degree of order S of the whole material is 0.4 or more, and, L1 0 type FeNi ordered alloy coercive force Hc is 87.5kA / m or more is obtained.
  • Comparative Example S1 the same FeNi disordered alloy as in Comparative Example S0 was used, nitriding was performed at 300 ° C. for 4 hours, denitrification was not performed, and evaluation was performed by X-ray diffraction.
  • Comparative Example S2 the same FeNi disordered alloy as in Comparative Example S0 was used, nitriding was not performed, denitrification was performed at 300 ° C. for 4 hours, and evaluation was performed by X-ray diffraction.
  • Comparative Example S3 the same FeNi disordered alloy as in Comparative Example S0 was used, subjected to nitriding treatment at 300 ° C. for 4 hours, denitrification treatment at 300 ° C. for 4 hours, and evaluated by X-ray diffraction.
  • Comparative Example S4 a FeNi disordered alloy produced by the flame spray method was used, and nitriding treatment and denitrogenating treatment were performed in the same manner as in Comparative Example S3, and evaluated by X-ray diffraction.
  • Comparative Example S5 a FeNi disordered alloy produced by a coprecipitation method was used, and nitriding treatment and denitrification treatment were performed in the same manner as in Comparative Example S3, and evaluation was performed by X-ray diffraction.
  • Comparative Examples S6, S7, S8, and S9 were performed in the same manner as Comparative Example S3, except that the nitriding treatment temperature was changed to 325 ° C, 350 ° C, 400 ° C, and 500 ° C. Further, in Comparative Examples S10, S11, S12, S13, S14, S15, and S16, the denitrification treatment temperature was changed to 150 ° C., 200 ° C., 250 ° C., 350 ° C., 400 ° C., 450 ° C., and 500 ° C. Except for this, the same procedure as in Comparative Example S3 was performed.
  • Comparative Example S17 Examples S18, S19, S20, S21, S22, S23, and S24, those having a volume average particle diameter of 30 nm to 140 nm were used, and the nitriding treatment was performed at a temperature of 300 ° C. for 50 hours for a long time. Nitrogen treatment is performed at 300 ° C. for 1 hour. The other conditions are the same as in Comparative Example S3.
  • the basic diffraction P2 appears, but the superlattice diffraction P1 does not appear. 6 and 7, the X-ray is assumed to be an Fe k ⁇ ray (wavelength: 1.7565365).
  • the estimate of the order parameter S were based on the method described in Patent Document 1. Estimates of the order parameter S can be estimated by estimated expression rules of S in L1 0 type FeNi ordered alloy shown in Equation 1 below.
  • Equation 1 “I sup ” is the integrated intensity of the peak of the superlattice diffraction P1 and “I fund ” is the integrated intensity of the peak of the basic diffraction P2. “(I sup / I fund ) obs ” is a ratio between the integrated intensity of the superlattice diffraction P1 and the integrated intensity of the basic diffraction P2 in the X-ray diffraction patterns measured in the examples and comparative examples. “(I sup / I fund ) cal ” is a ratio between the integrated intensity of the superlattice diffraction P1 and the integrated intensity of the basic diffraction P2 in the X-ray diffraction pattern of FIG. Then, as shown in Equation 1, the square root of both ratios is obtained as the regularity S.
  • FIGS. 8, 9, 10, and 11 For each of the examples and comparative examples, some of typical examples of measured X-ray diffraction patterns are shown in FIGS. 8, 9, 10, and 11.
  • FIG. Together it explained whether L1 0 type FeNi ordered alloy on the basis of the X-ray diffraction pattern is obtained, a description will be given of the relationship between the degree of order S and coercivity Hc.
  • the degree of order S is 0 because Comparative Examples S0 and S2 are not FeNi ordered alloys, and the coercive force Hc is 10.2 kA / m and 4.0 kA, respectively. The value was as small as / m.
  • Comparative Example S3 the regularity S was a relatively large value of 0.52, but the coercive force Hc could not be as large as 33.3 kA / m.
  • Comparative Example S3 in which both nitriding treatment and denitrification treatment were performed, peaks of superlattice diffraction P1 at 28 ° and 40 ° clearly appear. This superlattice diffraction P1 did not appear in Comparative Example S1 where no treatment was performed.
  • the peak marked with a black circle in Comparative Example S1 appears at a position different from superlattice diffraction P1, but this is FeNi nitride, not superlattice diffraction P1.
  • Comparative Example S1 is a nitride of FeNi that is subjected to nitriding treatment but not denitrifying treatment. As shown in FIG. 4, in Comparative Example S1, since the FeNi ordered alloy was not used, the degree of order was 0 and the coercive force Hc was a small value of 4.0 kA / m.
  • Comparative Examples S3, S4, and S5 are different from each other in the preparation method of the powder sample of FeNi disordered alloy and the volume average particle diameter, but in both cases, it exceeds 28 ° and 40 °.
  • the peak of the grating diffraction P1 appears clearly.
  • the difference in volume average particle diameter can be easily confirmed by observation with an electron microscope. In this way, by performing the nitriding treatment and denitrification treatment in a sample preparation method and the particle size is different, it can be produced L1 0 type FeNi ordered alloy.
  • FIG. 10 Comparative Examples S3, S4, and S5 are different from each other in the preparation method of the powder sample of FeNi disordered alloy and the volume average particle diameter, but in both cases, it exceeds 28 ° and 40 °.
  • the peak of the grating diffraction P1 appears clearly.
  • the difference in volume average particle diameter can be easily confirmed by observation with an electron microscope. In this way, by performing the nitriding treatment and denitrification
  • Example S21 the method for preparing the FeNi disordered alloy powder sample was substantially the same as Comparative Example S3, the nitriding time was 50 hours, and the denitrification time was 1 hour. Is. In Example S21, peaks of the superlattice diffraction P1 at 28 ° and 40 ° clearly appear. The volume average particle diameter is also relatively large at 140 nm. On the other hand, as shown in FIG. 4, the regularity S of Example S21 is a large value of 0.64, and the coercive force Hc is a large value of 150.6 kA / m. .
  • Comparative Examples S3 ⁇ S17 by performing the nitriding treatment and denitrification treatment, it is possible to produce the L1 0 type FeNi ordered alloy.
  • a certain degree of order S can be obtained, but a sufficient value cannot be obtained for the coercive force Hc.
  • too temperature of denitrification is low as in Comparative Example S10, when the temperature of the denitrification as in Comparative Example S15, S16 is too high, that the production of L1 0 type FeNi ordered alloy The degree of order S was 0 and the coercive force Hc was small.
  • FIG. 12 shows the relationship between the regularity S and the denitrification treatment temperature for the same sample and the comparative examples S6 and S10 to S16 subjected to the nitridation treatment except for the denitrification treatment temperature.
  • the treatment temperature for the denitrification treatment is preferably 250 ° C. or more and 400 ° C. or less.
  • the degree of order S was achieved to be 0.4 or more.
  • the regularity S is 0.5 or more, which is larger.
  • the degree of order S was 0.4 or more in Comparative Example S17 and Examples S18 to S24 in which the treatment temperature of the denitrification treatment was 250 ° C. or more and 400 ° C. or less. .
  • the denitrification treatment time may be as short as one hour or less.
  • Comparative Examples S3, S4, S6 to S9, S12 to S14, S17 and Examples S18 to S24 in FIG. 4 it is desirable whether it is performed for 4 hours or 1 hour.
  • the degree of regularity S can be obtained.
  • the coercive force Hc could be 87.5 kA / m or more even if the denitrification time was short.
  • the coercive force Hc may not exceed 87.5 kA / m regardless of the time of denitrification. From these, it was confirmed that from the viewpoint of the degree of order S and the coercive force Hc, the time for the denitrification treatment may be short if the denitrification treatment can be performed to produce the FeNi ordered alloy. .
  • the results shown in FIG. 4 indicate that the nitriding treatment temperature is preferably 300 ° C. or more and 500 ° C. or less.
  • the nitriding treatment temperature is in the range of 300 ° C. or more and 500 ° C. or less, the FeNi ordered alloy is obtained in any case. It was. For this reason, it can be said that an FeNi ordered alloy can be obtained within this temperature range.
  • the nitriding treatment time was not sufficient if it was short. That is, as in the comparative examples S12 to S14 in FIG. 4, when the processing temperature of nitriding is 325 ° C., the order S is 0.4 or more even when the processing time is 4 hours, but the coercive force Hc was less than 87.5 kA / m. On the other hand, as in Examples S18 to S24, when the processing temperature of nitriding is 300 ° C. and the processing time is 50 hours, the degree of order S is 0.4 or more and the coercive force Hc is 87. It was as large as 0.5 kA / m or more, and the magnetic properties were excellent.
  • the nitriding treatment time is an important factor in achieving a high coercive force Hc.
  • the coercive force Hc was 87.5 kA / m or more. This time slightly changes depending on the temperature of the nitriding treatment, and the processing time can be slightly shortened as the processing temperature is higher, but the processing time is set to 10 hours or more at 300 ° C. which is the lowest suitable temperature range for nitriding treatment. A large coercive force Hc could be obtained. For this reason, at a temperature higher than 300 ° C., the coercive force Hc can be 87.5 kA / m or more if the treatment time is at least 10 hours or more.
  • examples of nitriding treatment temperatures are 300 ° C., 325 ° C., 350 ° C., 400 ° C., and 500 ° C.
  • the nitriding treatment temperature is However, it is not limited to these examples.
  • the temperature of the nitriding treatment may be at least 300 ° C. or more and 500 ° C. or less, and may be a wider temperature range.
  • the coercive force Hc is also affected by the volume average particle diameter. Specifically, the coercive force Hc increases as the volume average particle size increases. As shown in FIG. 4, as shown in Comparative Example S17 and Examples S18 to S24, the coercive force Hc increases as the volume average particle size increases. When the volume average particle size is 30 nm as in Comparative Example S17, the coercive force Hc is 58.1 kA / m, which is a relatively large value, but it can be used as a magnet material or a magnetic recording material. It wasn't.
  • the coercive force Hc can be a large value of 87.5 kA / m or more.
  • the volume average particle diameter basically, the larger the coercive force Hc, the larger the coercive force Hc.
  • the coercive force Hc decreases thereafter. For example, when the thickness exceeds 250 nm, some of the coercive force Hc is reduced. For this reason, it is desirable that the volume average particle diameter is not too large.
  • the volume average particle diameter may exceed 250 nm, but for example, if the volume average particle diameter is 60 nm or more and 250 nm or less, the desired coercive force Hc can be realized more reliably.
  • the degree of order S and the coercive force Hc are also closely related. That is, as the degree of order S increases, the coercive force Hc also increases.
  • the degree of order S when the regularity S is 0.4 or more, it is possible to manufacture a coercive force Hc of 87.5 kA / m.
  • the degree of order S is 0.6 or more, a product having a coercive force Hc of 87.5 kA / m or more can be manufactured.
  • the desired coercive force Hc may not be obtained if the regularity S is large, but basically the larger the regularity S, the larger the coercive force Hc. Is possible.
  • the degree of order S when the degree of order S is 0.7 or more, the coercive force Hc can be 95.5 kA / m (1200 [Oe]) or more.
  • the FeNi ordered alloy has a degree of order S of 0.4 or more and a coercive force Hc of 87.5 kA / m or more, it is also used as a magnet material or a magnetic recording material. be able to.
  • the degree of order S is 0.7 or more and the coercive force Hc is 95.5 kA / m, it is possible to obtain a good magnetic material or magnetic recording material having a higher coercive force Hc.
  • particles of L1 0 type FeNi ordered alloy having such a high degree of order S and coercive force Hc as a magnetic powder it is possible to obtain a FeNi ordered alloy magnet by the magnet shape compacted the magnetic particles.
  • the FeNi ordered alloy magnet formed in this way can be applied as a magnet for a motor mounted on a vehicle, for example.
  • a magnetic tape serving as a magnetic recording medium can be constituted by applying FeNi ordered alloy particles to a tape-like film. Since the FeNi ordered alloy obtained as in the present embodiment has a high coercive force Hc, when it is used as a magnetic body of a magnetic recording medium, it is suppressed that stored data is rewritten by an environmental magnetic field. it can.
  • a nitriding treatment for nitriding the FeNi disordered alloy 100 may be performed, followed by a denitrification treatment for removing nitrogen from the nitridated FeNi disordered alloy.
  • the treatment temperature is set to 300 ° C. to 500 ° C.
  • the treatment time is set to 10 hours or more
  • the treatment temperature is set to 250 ° C. to 400 ° C.
  • a composition tends to form an L1 0 type FeNi ordered alloy.
  • high ordering with an order S of 0.4 or more is realized in an alloy having a composition range of Fe: 55 to 47 atomic%. .
  • the sample shape of the FeNi disordered alloy is not specified, it is desirable to be a powder sample as described above in order to shorten the nitriding treatment and the denitrification treatment.
  • the FeNi disordered alloy is a nanoparticle sample in order to perform these processes quickly.
  • an FeNi ordered alloy with higher coercive force Hc can be obtained by setting the volume average particle size to 45 nm or more.
  • the ordering of the powders of FeNi disordered alloys having different production methods is confirmed.
  • the production method of the disordered alloy is not limited to the above-described thermal plasma method, flame spray method, and coprecipitation method.
  • nitriding treatment conditions and removal are performed using irregular alloys produced by flame spraying methods other than the thermal plasma method and coprecipitation methods. Even when the nitrogen conditions are the conditions of Examples S18 to S24, the same results as those of these Examples are obtained.
  • the nitrogen concentration in the nitride treated nitride, Fe about 33 atomic% to 20 atomic% as atomic weight ratio to the total amount of Ni and nitrogen is preferable.
  • L1 can be performed without mixing impurities by performing nitridation with ammonia gas and denitrification with hydrogen gas.
  • a zero- type FeNi ordered alloy can be obtained.
  • Hc can be the L1 0 type FeNi ordered alloy of high as or higher 87.5kA / m. This is a simple method both in terms of apparatus and process as compared with the conventional laminating method by molecular beam epitaxy and the method of heat treatment while irradiating with neutrons. Therefore, according to the present embodiment, the L1 0 type FeNi ordered alloy having a desired degree of order S and coercivity Hc, it can be easily synthesized.
  • the present embodiment when forming the L1 0 type FeNi ordered alloy from FeNi disordered alloy, further increasing the degree of order S by generating an intermediate product.
  • nitriding and denitrifying are performed, but in this embodiment, FeNiN is generated as an intermediate product when nitriding is completed.
  • the oxide film formed on the surface of the FeNi disordered alloy is removed prior to the nitriding treatment so that the intermediate product is accurately generated by the nitriding treatment.
  • FeNi disordered alloy is subjected to nitriding treatment, and nitrogen is taken into the II site shown in FIG. 1 to form FeNiN as an intermediate product containing a large amount of Ni at the II site. To do. Then, a denitrification, by releasing nitrogen from II site, constituting the L1 0 type FeNi ordered alloy.
  • an FeNi irregular alloy is prepared. Since the oxide film is formed on the surface of the FeNi disordered alloy, a removal process for removing the oxide film on the surface of the FeNi disordered alloy is performed prior to the nitriding process. Thereafter, a nitriding process is performed following the removal process.
  • a heat treatment is performed at 300 ° C. to 450 ° C., for example, in an oxide film etching atmosphere.
  • the oxide film on the surface of the FeNi disordered alloy is removed, and the surface state is easily nitrided.
  • heat treatment is performed in an atmosphere containing N, for example, at 200 ° C. to 400 ° C.
  • the FeNi disordered alloy that has been easily nitrided by removing the oxide film can be precisely nitrided, and FeNiN as an intermediate product is formed.
  • the nitriding treatment here is performed after removing the oxide film, so that the nitriding reaction is easier, and the temperature may be lower than in the case of the first embodiment. For this reason, the temperature of the nitriding treatment is set to 200 ° C. to 400 ° C., but this temperature may be exceeded, and it may be set to 500 ° C. or less as in the first embodiment.
  • denitrification treatment is performed on FeNiN as an intermediate product.
  • heat treatment is performed at 200 to 400 ° C. in a denitrification atmosphere, for example.
  • L1 0 type FeNi ordered alloy it is possible to form an L1 0 type FeNi ordered alloy.
  • the above-mentioned removal treatment is performed nitridation treatment and denitrification, a specific example of when forming an L1 0 type FeNi ordered alloy.
  • the removal process and the nitriding process were performed according to the profile shown in FIG. 15A.
  • a heating furnace such as the tubular furnace 10 or the muffle furnace described above was prepared, and a FeNi irregular alloy nanoparticle sample having an average particle diameter of 30 nm was placed in the heating furnace. Then, the heating furnace was heated from room temperature to a temperature at the time of removal treatment for removing the oxide film, here 400 ° C. At this time, in order to suppress the oxidation of the nanoparticle sample due to oxygen present in the heating furnace, an inert gas was introduced. Here, the temperature raising step was performed while introducing N 2 (nitrogen). .
  • N 2 that can be used in the subsequent nitriding treatment is used.
  • an inert gas other than N 2 such as Ar (argon) or He (helium), is used. Also good.
  • the time required for removing the oxide film is arbitrary, but it has been confirmed that the oxide film can be removed to some extent by performing, for example, a time of 10 minutes or more.
  • the temperature for removing the oxide film may be at least between 300 ° C. and 450 ° C.
  • the lower limit of the temperature for removing the oxide film is set to 300 ° C. because it has been confirmed that the oxide film can be removed if it is at least 300 ° C. or higher. However, even if it is less than 300 ° C., it is considered that the oxide film can be removed over time.
  • the upper limit value of the temperature for removing the oxide film is defined in order to facilitate the subsequent nitriding of the FeNi disordered alloy. That is, when the temperature for removing the oxide film is higher than 450 ° C., the surface of the FeNi disordered alloy from which the oxide film has been removed is sintered and is not easily nitrided. Accordingly, the temperature is set to 450 ° C.
  • the rate of introduction of the etching gas into the heating furnace is also arbitrary.
  • the oxide film can be removed if it is in the range of at least 0.3 to 5 L / min.
  • the nitriding process was continuously performed in the same heating furnace. Specifically, the gas introduced into the heating furnace was switched from the etching gas to the nitriding gas, the atmosphere inside the heating furnace was made to contain N, and the temperature necessary for nitriding was maintained. In this experiment, NH 3 (ammonia) was used as the nitriding gas, which was introduced into the heating furnace at a rate of 5 L / min, and the heating furnace was maintained at 300 ° C. for 50 hours. Thereby, the nanoparticle sample was nitrided, and FeNiN as an intermediate product was formed.
  • NH 3 ammonia
  • the time required for the nitriding treatment is arbitrary, for example, it has been confirmed that FeNiN as an intermediate product can be synthesized by performing for 10 hours.
  • the nitriding temperature may be at least between 200 ° C. and 400 ° C.
  • the introduction rate of the nitriding gas into the heating furnace for generating the atmosphere containing N is also arbitrary.
  • the nanoparticle sample is nitrided at least in the range of 0.1 to 10 L / min. did it.
  • the nitridation process was performed subsequently to the oxide film removal process. By doing so, it is possible to suppress the formation of an oxide film again on the surface of the FeNi disordered alloy from which the oxide film has been removed, and it is not necessary to perform the temperature raising process again, simplifying the heat treatment and shortening the time. Can be achieved.
  • denitrification was performed.
  • the process according to the profile shown to FIG. 15B was performed.
  • denitrification is performed after a nitridation process, but it is also possible to perform these continuously.
  • a heating furnace such as the tubular furnace 10 or the muffle furnace described above was prepared, and FeNiN as an intermediate product generated according to the profile of FIG. 15A was placed in the heating furnace. And the heating furnace was heated up from room temperature to the temperature at the time of a denitrification process, 300 degreeC here. In this case, in order to FeNiN an intermediate product by oxygen present in the heating furnace is prevented from being oxidized, and introducing an inert gas, subjected to heated process while introducing N 2 here It was.
  • the temperature of the denitrification treatment may be at least between 200 ° C. and 400 ° C.
  • an arbitrary even the introduction rate of the gas into the heating furnace to generate an atmosphere denitrification can be performed, for example, in the case of H 2, denitrification treatment be in the range of at least 0.1 ⁇ 5L / min Was done.
  • L1 0 type FeNi ordered alloy By performing the denitrification treatment as described above, we were able to generate L1 0 type FeNi ordered alloy.
  • This so-formed L1 0 type FeNi ordered alloy was determined an average order parameter S of the whole material. Specifically, the regularity S was determined from the powder X-ray diffraction pattern.
  • X-ray diffraction pattern of the powder of L1 0 type FeNi ordered alloy when the degree of order S is 1, is represented as shown in FIG. 16.
  • the regularity S is the integrated intensity of the diffraction peak from the (001) plane that is the superlattice reflection, that is, the peak of the superlattice diffraction, and the diffraction peak from the (111) plane, that is, the fundamental diffraction of the X-ray diffraction pattern.
  • FIG. 17 shows the relationship with the diffraction intensity ratio, which is the ratio with the integrated intensity of the peak. Therefore, for the FeNi ordered alloy on to the generated L1 0 type and as in this embodiment, obtaining the X-ray diffraction pattern, it is possible to obtain a degree of order S from the result.
  • FeNi irregular after performing removal processing of oxide film from the alloy subjected to nitriding treatment to generate a FeNiN an intermediate product, L1 0 type further performing denitrification X-ray diffraction pattern was obtained when an FeNi ordered alloy was produced.
  • FIG. 18 shows the result.
  • the L1 0 type FeNi ordered alloy produced by the production method of the present embodiment it was possible to obtain a high degree of order S. Furthermore, this L1 0 type FeNi ordered alloy, where also performed magnetic characterization, it was possible to obtain a relatively high value of 1120kA / m as anisotropy field.
  • the present embodiment generates a FeNi an intermediate product by performing a nitriding process on disordered alloy Fenin, it generates an L1 0 type FeNi ordered alloy further subjected to denitrification ing.
  • the average degree of order S of the whole it is possible to easily generate an L1 0 type FeNi ordered alloy as a high as 0.7 or more.
  • an intermediate product can be generated more accurately by performing a nitriding process after performing a removing process for removing the oxide film formed on the surface of the FeNi disordered alloy. . Therefore, by performing the removal processing, it is possible to obtain L1 0 type FeNi ordered alloy having a higher degree of order S.
  • the removal of the oxide film, the obtaining of an intermediate product by nitriding treatment, and the lowering of the nitriding treatment temperature can be made different from the first embodiment.
  • Other matters, such as the time for denitrification, the volume average particle diameter, etc., can be said to be the same as in the first embodiment.
  • the first embodiment an example of the conditions for nitriding and denitrifying has been described.
  • the degree of order S is 0.4 or more, and, if the coercive force Hc can be obtained FeNi ordered alloy of the above L1 0 type 87.5kA / m, these processes
  • the processing temperature and processing time are not limited to the above example.
  • examples of the conditions for the oxide film removal process, the nitriding process, and the denitrifying process have been described. However, these are merely examples of the respective conditions.
  • the degree of order S is 0.4 or more, and, if it is possible to coercive force Hc obtain 87.5kA / m or more L1 0 type FeNi ordered alloy, processing temperatures of these processes, the processing time, the It is not limited to the example.
  • the L1 0 type by performing the nitriding treatment and denitrification treatment, to obtain an L1 0 type FeNi ordered alloy
  • the L1 0 type by a method other than the nitriding treatment and denitrification
  • An FeNi ordered alloy may be obtained. That is, after performing the process of the Fe and Ni to synthesize compounds that are aligned in the same lattice structure as the L1 0 type FeNi ordered structure, by performing a process of removing unnecessary elements other than Fe and Ni from the compound in may be obtained an L1 0 type FeNi ordered alloy.
  • L1 0 type FeNi ordered alloy according to the embodiment is applied to a magnetic material such as magnetic materials and magnetic recording materials, the scope of the FeNi ordered alloy is not limited to a magnetic material .

Abstract

A FeNi ordered alloy having an L10-type ordered structure, the degree of order being at least 0.4, and the coercive force being at least 87.5 kA/m. For example, a FeNi disordered alloy is subjected to a nitriding treatment and then a denitrification treatment to thereby obtain an L10-type FeNi ordered alloy. With regard to the FeNi disordered alloy, the volume-average grain diameter is, e.g., at least 45 nm, and with regard to the nitriding treatment, the treatment temperature is, e.g., 300-500°C and the treatment time is at least 10 hours.

Description

ＦｅＮｉ規則合金、ＦｅＮｉ規則合金磁石およびＦｅＮｉ規則合金の製造方法FeNi ordered alloy, FeNi ordered alloy magnet and method for producing FeNi ordered alloy 関連出願への相互参照Cross-reference to related applications
　本出願は、２０１７年４月１３日に出願された日本特許出願番号２０１７－８００２５号に基づくもので、ここにその記載内容が参照により組み入れられる。 This application is based on Japanese Patent Application No. 2017-80025 filed on Apr. 13, 2017, the contents of which are incorporated herein by reference.
　本開示は、Ｌ１０型の規則構造を有するＬ１０型のＦｅＮｉ規則合金、および、このようなＬ１０型のＦｅＮｉ規則合金を用いて構成したＦｅＮｉ規則合金磁石に関する。 The present disclosure, L1 0 type FeNi ordered alloy having an L1 0 type ordered structure, and to a FeNi ordered alloy magnet which is constructed by using such a L1 0 type FeNi ordered alloy.
　Ｌ１０型（エルワンゼロ型）のＦｅＮｉ（鉄－ニッケル）規則合金は、レアアースや貴金属を全く使用しない磁石材料および磁気記録材料として期待されている。ここで、Ｌ１０型規則構造とは、面心立方格子を基本としてＦｅとＮｉとが（００１）方向に層状に配列した結晶構造である。このようなＬ１０型規則構造は、ＦｅＰｔ、ＦｅＰｄ、ＡｕＣｕなどの合金にみられ、通常、不規則合金を規則－不規則転移温度Ｔλ以下で熱処理し、拡散を促すことで得られる。 L1 0 type (Eruwanzero type) of FeNi (iron - nickel) ordered alloy is expected as a magnet material and magnetic recording material uses no rare earth and precious metals. Here, the L1 0 type ordered structure is a crystal structure in which Fe and Ni are arranged in layers in the (001) direction based on a face-centered cubic lattice. Such L1 0 ordered structure is, FePt, FePd, seen in alloys such AuCu, usually, a disordered alloy rules - heat treatment at below disorder transition temperature t [lambda, obtained by prompting diffusion.
　しかし、Ｌ１０型のＦｅＮｉ規則合金を得るための転移温度Ｔλは３２０℃と低温であり、この温度以下では拡散が極めて遅いため熱処理のみで合成することは困難である。そこで、従来より、Ｌ１０型のＦｅＮｉ規則合金を合成するための様々な試みがなされている。 However, the transition temperature Tλ to obtain L1 0 type FeNi ordered alloy is 320 ° C. and cold, it is difficult at this temperature following synthesizing only the heat treatment for diffusion is very slow. Therefore, conventionally, various attempts to synthesize the L1 0 type FeNi ordered alloy have been made.
　具体的に、従来では、非特許文献１に記載のような、分子線エピタキシー（略称：ＭＢＥ）を用いてＦｅとＮｉの単原子膜を交互に積層する手法や、その他、中性子を照射しながら磁場中で熱処理を行う手法等も提案されている。 Specifically, conventionally, as described in Non-Patent Document 1, molecular beam epitaxy (abbreviation: MBE) is used to alternately stack Fe and Ni monoatomic films, and in addition, while irradiating with neutrons A method of performing heat treatment in a magnetic field has also been proposed.
　しかしながら、上記非特許文献１のような分子線エピタキシーを用いた方法や中性子照射を用いた方法といった従来の方法で得られるＬ１０のＦｅＮｉ規則合金の規則度は、最大で０．４程度と全体的には小さいものとなっている。また、ＦｅＮｉ規則合金の材料の全体において規則度が最大となるのではなく、局所的に規則度が高くなる部分があるだけである。さらに、得られたＦｅＮｉ規則合金の保磁力については、ＦｅＮｉ規則合金を磁石材料や磁気記録材料として用いることができる程度に大きなものではない。例えば、磁気記録材料としては、環境磁場によって保存データが書き換えられてしまわない程度の保磁力が要求される。 However, rules of the above non-patent conventional methods L1 0 of FeNi ordered alloy obtained by such methods such using methods and neutron irradiation using molecular beam epitaxy as document 1, 0.4 degree and a total of up to In fact, it is small. In addition, the degree of ordering is not maximized in the entire material of the FeNi ordered alloy, but there is only a portion where the degree of ordering is locally high. Further, the coercive force of the obtained FeNi ordered alloy is not so large that the FeNi ordered alloy can be used as a magnet material or a magnetic recording material. For example, a magnetic recording material is required to have a coercive force that does not rewrite stored data by an environmental magnetic field.
　本開示は、磁石材料や磁気記録材料としても用いることができるＦｅＮｉ規則合金を提供することや、それを用いて構成されるＦｅＮｉ規則合金磁石を提供することを目的とする。 The present disclosure aims to provide an FeNi ordered alloy that can be used also as a magnet material and a magnetic recording material, and to provide an FeNi ordered alloy magnet constituted by using the FeNi ordered alloy.
　本開示の第１の観点におけるＦｅＮｉ規則合金は、Ｌ１０型の規則構造を有し、材料の全体の平均的な規則度が０．４以上、かつ、保磁力が８７．５ｋＡ／ｍ以上とされている。 FeNi ordered alloy of the first aspect of the present disclosure includes an L1 0 type ordered structure, the average degree of order of the overall material is 0.4 or more and a coercive force 87.5kA / m or more and Has been.
　このように、規則度が０．４以上、かつ、保磁力が８７．５ｋＡ／ｍ以上のＦｅＮｉ規則合金とすることで、磁石材料や磁気記録材料としても用いることが可能なＦｅＮｉ規則合金とすることができる。例えば、このようなＦｅＮｉ規則合金を用いて、ＦｅＮｉ規則合金磁石とすることができる。 Thus, by using a FeNi ordered alloy having a degree of order of 0.4 or more and a coercive force of 87.5 kA / m or more, a FeNi ordered alloy that can also be used as a magnet material or a magnetic recording material is obtained. be able to. For example, an FeNi ordered alloy magnet can be obtained using such an FeNi ordered alloy.
　本開示の第２の観点におけるＦｅＮｉ規則合金の製造方法では、ＦｅＮｉ不規則合金（１００）を窒化する窒化処理を行うことと、窒化処理されたＦｅＮｉ不規則合金から窒素を除去する脱窒素処理を行うことにより、規則度が０．４以上、かつ、保磁力が８７．５ｋＡ／ｍ以上であるＬ１０型のＦｅＮｉ規則合金を得ることと、を含み、窒化処理を行うことでは、窒化処理の処理温度を３００℃以上５００℃以下とし、処理時間を１０時間以上とする。 In the method for producing an FeNi ordered alloy according to the second aspect of the present disclosure, a nitriding process for nitriding the FeNi disordered alloy (100) and a denitrification process for removing nitrogen from the nitridated FeNi disordered alloy are performed. by performing, rule of 0.4 or more, and includes a possible coercive force obtain L1 0 type FeNi ordered alloy is 87.5kA / m or more, and is by performing nitriding treatment, the nitriding The treatment temperature is 300 ° C. or more and 500 ° C. or less, and the treatment time is 10 hours or more.
　このようなＦｅＮｉ規則合金の製造方法により、材料の全体の平均的な規則度が０．４以上、かつ、保磁力が８７．５ｋＡ／ｍ以上となるＬ１０型のＦｅＮｉ規則合金を、容易に合成することができる。 The method of manufacturing such a FeNi ordered alloy, the overall average degree of order of 0.4 or more materials, and the L1 0 type FeNi ordered alloy coercivity is 87.5kA / m or more, easily Can be synthesized.
　本開示の第３の観点におけるに記載のＦｅＮｉ規則合金の製造方法では、ＦｅとＮｉとがＬ１０型のＦｅＮｉ規則構造と同じ格子構造で整列した化合物を合成することと、化合物からＦｅとＮｉ以外の不要な元素を除去することでＬ１０型のＦｅＮｉ規則合金を生成することと、を含み、化合物を合成することでは、処理温度を２００℃以上５００℃以下とし、処理時間を１０時間以上として、ＦｅＮｉ不規則合金を窒化処理することで化合物として中間生成物となるＦｅＮｉＮを合成する。 In the manufacturing method of the FeNi ordered alloy according to definitive to a third aspect of the present disclosure, the method comprising synthesizing the compound of Fe and Ni are aligned in the same lattice structure as the L1 0 type FeNi ordered structure, Fe and Ni from compound anda generating an L1 0 type FeNi ordered alloy by removing unnecessary elements other than, by combining the compound, the process temperature of 200 ° C. or higher 500 ° C. or less, the treatment time over 10 hours As a compound, FeNiN as an intermediate product is synthesized as a compound by nitriding the FeNi disordered alloy.
　このように、ＦｅとＮｉとがＬ１０型のＦｅＮｉ規則構造と同じ格子構造で整列した化合物を合成し、この化合物からＬ１０型のＦｅＮｉ規則合金を生成する。このような製造方法により、材料の全体の平均的な規則度が０．４以上、かつ、保磁力が８７．５ｋＡ／ｍ以上となるＬ１０型のＦｅＮｉ規則合金を、容易に合成することができる。
　なお、各構成要素等に付された括弧付きの参照符号は、その構成要素等と後述する実施形態に記載の具体的な構成要素等との対応関係の一例を示すものである。 Thus, to synthesize a compound of Fe and Ni are aligned in the same lattice structure as the L1 0 type FeNi ordered structure, and generates an L1 0 type FeNi ordered alloy from this compound. By such a manufacturing method, the average degree of order of the overall material is 0.4 or more, and an L1 0 type FeNi ordered alloy coercivity is 87.5kA / m or more, it can be readily synthesized it can.
Reference numerals in parentheses attached to each component and the like indicate an example of a correspondence relationship between the component and the like and specific components described in the embodiments described later.
Ｌ１０型のＦｅＮｉ規則構造の格子構造を示した模式図である。L1 is a schematic diagram showing a 0-type lattice structure of FeNi ordered structure of. 規則度Ｓ＝０となるＦｅＮｉ不規則合金から規則度Ｓ＝１となるＦｅＮｉ超格子にかけて規則度Ｓ毎のＦｅＮｉ合金の格子構造の様子を示した模式図である。It is the schematic diagram which showed the mode of the lattice structure of the FeNi alloy for every degree of order S from the FeNi disordered alloy in which degree of order S = 0 to the FeNi superlattice in which degree of order S = 1. 保磁力Ｈｃの測定用サンプル成形の様子を示した斜視図である。It is the perspective view which showed the mode of the sample shaping | molding for the measurement of the coercive force Hc. 第１実施形態にかかる実施例および比較例の製造条件および評価結果を示す図表である。It is a graph which shows the manufacture conditions and evaluation result of the Example concerning 1st Embodiment, and a comparative example. 第１実施形態にかかる実施例および比較例におけるＦｅＮｉ規則合金の製造に用いた製造装置の構成を模式的に示す図である。It is a figure which shows typically the structure of the manufacturing apparatus used for manufacture of the FeNi ordered alloy in the Example concerning 1st Embodiment, and a comparative example. 規則度Ｓが１であるＬ１０型のＦｅＮｉ規則合金のＸ線回折パターンのシミュレーション結果を示す図である。Degree of order S is a diagram showing a simulation result of X-ray diffraction pattern of the L1 0 type FeNi ordered alloy is 1. ＦｅＮｉ不規則合金のＸ線回折パターンのシミュレーション結果を示す図である。It is a figure which shows the simulation result of the X-ray diffraction pattern of a FeNi disordered alloy. 比較例Ｓ０、Ｓ２、Ｓ３におけるＦｅＮｉ規則合金のＸ線回折パターンの測定結果を示す図である。It is a figure which shows the measurement result of the X-ray-diffraction pattern of the FeNi ordered alloy in comparative example S0, S2, S3. 比較例Ｓ１、Ｓ３におけるＦｅＮｉ規則合金のＸ線回折パターンの測定結果を示す図である。It is a figure which shows the measurement result of the X-ray-diffraction pattern of the FeNi ordered alloy in comparative example S1, S3. 比較例Ｓ３、Ｓ４、Ｓ５におけるＦｅＮｉ規則合金のＸ線回折パターンの測定結果を示す図である。It is a figure which shows the measurement result of the X-ray-diffraction pattern of the FeNi ordered alloy in comparative example S3, S4, S5. 実施例Ｓ２１におけるＦｅＮｉ規則合金のＸ線回折パターンの測定結果を示す図である。It is a figure which shows the measurement result of the X-ray-diffraction pattern of the FeNi ordered alloy in Example S21. 上記の実施例および比較例におけるＦｅＮｉ規則合金について、規則度Ｓと脱窒素処理の処理温度との関係を示すグラフである。It is a graph which shows the relationship between the order degree S and the processing temperature of a denitrification process about the FeNi ordered alloy in said Example and a comparative example. 図４に示す実施例および比較例について、規則度Ｓと保磁力Ｈｃとの関係をプロットした図である。It is the figure which plotted the relationship between the regularity S and the coercive force Hc about the Example and comparative example which are shown in FIG. ＦｅＮｉ不規則合金を窒化処理を行って中間生成物を生成してから脱窒素処理を行う場合の格子構造の様子を示した模式図である。It is the schematic diagram which showed the mode of the grating | lattice structure in the case of performing a denitrification process after producing | generating an intermediate product by nitriding a FeNi irregular alloy. 酸化膜の除去処理と窒化処理のプロファイルを示したタイムチャートである。It is the time chart which showed the profile of the removal process of an oxide film, and the nitriding process. 脱窒素処理のプロファイルを示したタイムチャートである。It is the time chart which showed the profile of the denitrification process. 規則度Ｓが１である場合におけるＬ１０型のＦｅＮｉ規則合金の粉末のＸ線回折パターンを示す図である。Degree of order S is a diagram showing an X-ray diffraction pattern of the powder of L1 0 type FeNi ordered alloy when it is 1. 規則度Ｓと回折強度比との関係を示したグラフである。It is the graph which showed the relationship between the regularity S and diffraction intensity ratio. 第２実施形態の製造方法によって製造したＬ１０型のＦｅＮｉ規則合金のＸ線回折パターンの測定結果を示す図である。Is a graph showing measurement results of X-ray diffraction pattern of the L1 0 type FeNi ordered alloy manufactured by the manufacturing method of the second embodiment.
　以下、本開示の実施形態について図に基づいて説明する。なお、以下の各実施形態相互において、互いに同一もしくは均等である部分には、同一符号を付して説明を行う。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In the following embodiments, parts that are the same or equivalent to each other will be described with the same reference numerals.
　（第１実施形態）
　第１実施形態について説明する。本実施形態にかかるＬ１０型のＦｅＮｉ規則合金、すなわちＦｅＮｉ超格子は、磁石材料および磁気記録材料等の磁性材料に適用されるものであり、規則度Ｓが０．４以上で、保磁力Ｈｃが８７．５ｋＡ／ｍ以上と大きく、磁性特性に優れたものである。 (First embodiment)
A first embodiment will be described. L1 0 type FeNi ordered alloy according to the present embodiment, i.e. FeNi superlattice is intended to be applied to a magnetic material such as magnetic materials and magnetic recording materials, in the degree of order S is 0.4 or more, the coercive force Hc Is as large as 87.5 kA / m or more and has excellent magnetic properties.
　ここでいう規則度Ｓとは、ＦｅＮｉ超格子における規則化の度合を示している。上記したように、Ｌ１０型規則構造は、面心立方格子を基本とした構造となっており、図１に示すような格子構造を有している。この図において、面心立方格子の［００１］面の積層構造における最も上面側の層をＩサイト、最も上面側の層と最も下面側の層との間に位置している中間層をＩＩサイトとする。この場合、Ｉサイトに金属Ａが存在する割合をｘ、金属Ｂが存在する割合を１－ｘとすると、Ｉサイトにおける金属Ａと金属Ｂが存在する割合はＡｘＢ１－ｘと表される。同様に、ＩＩサイトに金属Ｂが存在する割合をｘ、金属Ａが存在する割合を１－ｘとすると、ＩＩサイトにおける金属Ａと金属Ｂが存在する割合はＡ１－ｘＢｘと表される。なお、ｘは、０．５≦ｘ≦１を満たす。そして、この場合において、規則度Ｓは、Ｓ＝２ｘ－１で定義される。 Here, the degree of order S indicates the degree of ordering in the FeNi superlattice. As described above, L1 0 ordered structure is a basic structure of the face-centered cubic lattice has a lattice structure as shown in FIG. In this figure, the uppermost layer in the [001] plane laminated structure of the face-centered cubic lattice is the I site, and the intermediate layer located between the uppermost layer and the lowermost layer is the II site. And In this case, if the ratio of the presence of metal A at the I site is x and the ratio of the presence of metal B is 1-x, the ratio of the presence of metal A and metal B at the I site is expressed as A x B 1-x. The Similarly, when the ratio of the presence of metal B at the II site is x and the ratio of the presence of metal A is 1-x, the ratio of the presence of metal A and metal B at the II site is expressed as A 1-x B x. The Note that x satisfies 0.5 ≦ x ≦ 1. In this case, the regularity S is defined as S = 2x-1.
　このため、例えば、金属ＡをＮｉ、金属ＢをＦｅとし、Ｎｉを白色、Ｆｅを黒色で表すと、ＦｅＮｉ合金における規則度Ｓは、規則度Ｓ＝０となるＦｅＮｉ不規則合金から規則度Ｓ＝１となるＦｅＮｉ超格子にかけて図２のように表わされる。なお、すべて白色となっているものは、Ｎｉが１００％、Ｆｅが０％となっていることを示し、すべて黒色となっているものは、Ｎｉが０％、Ｆｅが１００％となっていることを示している。また、白色と黒色が半々のものはＮｉが５０％、Ｆｅが５０％となっていることを示している。 Therefore, for example, when the metal A is Ni, the metal B is Fe, Ni is white, and Fe is black, the order S in the FeNi alloy is the order S from the FeNi disordered alloy in which the order S = 0. FIG. 2 shows the FeNi superlattice where = 1. In addition, when all are white, it indicates that Ni is 100% and Fe is 0%, and when all is black, Ni is 0% and Fe is 100%. It is shown that. In addition, the white and black ones indicate that Ni is 50% and Fe is 50%.
　このように表される規則度Ｓについて、例えばＩサイトでは金属ＡとなるＮｉに偏り、ＩＩサイトでは金属ＢとなるＦｅに偏るようにし、本実施形態のように全体の平均的な規則度Ｓが０．４以上になると良好な磁気特性を得ることが可能となる。ただし、規則度Ｓについては、材料全体において平均的に値が高くなっている必要があり、局所的に値が高くなっていても良好な磁気特性を得ることはできない。例えば、Ｌ１０型規則構造が構成する面心立方格子の各格子のすべてで規則度Ｓが所定値以上になっている必要があり、一部の格子が局所的に規則度Ｓが高いことによって見かけ上の規則度Ｓが同じになっても、磁気特性は良好にならない。このため、局所的に高い値であったとしても、ここでいう全体の平均的な規則度Ｓが０．４以上には含まれない。 The regularity S expressed in this way is, for example, biased toward Ni serving as metal A at the I site and biased toward Fe serving as metal B at the II site, and the overall average regularity S as in the present embodiment. When the value is 0.4 or more, good magnetic properties can be obtained. However, the degree of order S needs to be high on average throughout the material, and good magnetic properties cannot be obtained even if the value is locally high. For example, the regularity S needs to be equal to or higher than a predetermined value in all the lattices of the face-centered cubic lattice formed by the L1 0 type regular structure, and the regularity S is locally high in some lattices. Even if the apparent regularity S is the same, the magnetic properties are not improved. For this reason, even if it is a locally high value, the average average regularity S here is not included in 0.4 or more.
　また、保磁力Ｈｃとは、得られたＦｅＮｉ規則合金に対して磁場を印加し、ＦｅＮｉ規則合金の磁化方向が磁場の影響で切り替わるときの磁場の強さとして求められる。具体的には、図３中の（ａ）に示すように、内径２ｍｍ、高さ７ｍｍの有底円筒状の容器部１ａと外径２ｍｍ、高さ１５ｍｍの円柱状の棒状部１ｂとを有するサンプルホルダー１を用意する。そして、図３中の（ｂ）に示すように、容器部１ａ内にＦｅＮｉ規則合金の粒子を１０ｍｇ充填しつつ、図３中の（ｃ）に示すように、容器部１ａの開口部側から別のサンプルホルダー１の棒状部１ｂでＦｅＮｉ規則合金を押さえる。このようにして、容器部１ａ内において円柱形状に形状を固定したサンプル２を作成する。そして、そのＦｅＮｉ規則合金のサンプル２に対して、十分大きな磁場を印加しサンプル２の磁化がそれ以上大きくならないような飽和状態まで持っていく。その後先ほどとは逆方向の磁場を印加し、サンプル２の磁化がゼロになるタイミングを検出する。そのときの磁場の強さを保磁力Ｈｃとしている。例えば、Quantum Desighn社製の小型無冷媒型PPMS VersaLabを用い、磁場掃引速度１０[Ｏｅ]として磁場の強さを求めている。 Further, the coercive force Hc is obtained as the strength of the magnetic field when a magnetic field is applied to the obtained FeNi ordered alloy and the magnetization direction of the FeNi ordered alloy is switched by the influence of the magnetic field. Specifically, as shown in FIG. 3A, it has a bottomed cylindrical container portion 1a having an inner diameter of 2 mm and a height of 7 mm, and a columnar rod-like portion 1b having an outer diameter of 2 mm and a height of 15 mm. A sample holder 1 is prepared. Then, as shown in (b) of FIG. 3, while 10 mg of FeNi ordered alloy particles are filled in the container 1a, as shown in (c) of FIG. 3, from the opening side of the container 1a. The FeNi ordered alloy is pressed by the rod-like portion 1 b of another sample holder 1. In this way, the sample 2 whose shape is fixed in a cylindrical shape in the container portion 1a is created. Then, a sufficiently large magnetic field is applied to the FeNi ordered alloy sample 2 to bring it to a saturation state where the magnetization of the sample 2 does not increase any more. Thereafter, a magnetic field in the opposite direction to the previous one is applied, and the timing at which the magnetization of the sample 2 becomes zero is detected. The strength of the magnetic field at that time is defined as a coercive force Hc. For example, a small refrigerant-free PPMS VersaLab manufactured by Quantum Desighn is used, and the strength of the magnetic field is obtained at a magnetic field sweep rate of 10 [Oe].
　なお、保磁力Ｈｃは、ＳＩ単位ではｋＡ／ｍで表されるが、ＯＧＳ単位ではＯｅ［エルステッド］で表され、１Ａ／ｍ＝４π×１０－３［Ｏｅ］であるため、８７．５ｋＡ／ｍ＝１１００［Ｏｅ］である。 The coercive force Hc is expressed in kA / m in SI units, but is expressed in Oe [Oersted] in OGS units, and is 1A / m = 4π × 10 −3 [Oe], so 87.5 kA / m = 1100 [Oe].
　磁石材料や磁気記録材料としても用いることができるＦｅＮｉ規則合金であるためには、それらの材料に要求される保磁力Ｈｃを有していることが求められる。この保磁力Ｈｃについて本発明者らが鋭意検討を行ったところ、磁石材料や磁気記録材料としても用いるためには、ＦｅＮｉ規則合金の保磁力Ｈｃが８７．５ｋＡ／ｍ以上であることが必要であることが確認された。また、規則度Ｓと保磁力Ｈｃとは相関関係があり、ＦｅＮｉ規則合金の保磁力Ｈｃが８７．５ｋＡ／ｍ以上となるためにはＦｅＮｉ規則合金の全体の平均的な規則度Ｓが０．４以上であることが必要になることが確認された。 In order to be an FeNi ordered alloy that can also be used as a magnet material or a magnetic recording material, it is required to have a coercive force Hc required for these materials. As a result of extensive studies by the present inventors on the coercive force Hc, in order to use it as a magnet material or a magnetic recording material, it is necessary that the coercive force Hc of the FeNi ordered alloy is 87.5 kA / m or more. It was confirmed that there was. Further, there is a correlation between the degree of order S and the coercive force Hc. In order for the coercive force Hc of the FeNi ordered alloy to be 87.5 kA / m or more, the average order degree S of the entire FeNi ordered alloy is 0. It was confirmed that it was necessary to be 4 or more.
　このため、本実施形態では規則度Ｓが０．４以上、かつ、保磁力Ｈｃが８７．５ｋＡ／ｍ以上のＦｅＮｉ規則合金としている。また、ＦｅＮｉ規則合金の保磁力Ｈｃは、ＦｅＮｉ規則合金の粒径や製造方法にも依存していることも判った。より高い保磁力Ｈｃを得るためには、後述するように、ＦｅＮｉ規則合金の粒径や製造方法をより適したものとすることが望ましい。 Therefore, in this embodiment, the FeNi ordered alloy has a degree of order S of 0.4 or more and a coercive force Hc of 87.5 kA / m or more. It was also found that the coercive force Hc of the FeNi ordered alloy depends on the grain size of the FeNi ordered alloy and the manufacturing method. In order to obtain a higher coercive force Hc, it is desirable to make the grain size and manufacturing method of the FeNi ordered alloy more suitable as described later.
　このようなＬ１０型のＦｅＮｉ規則合金は、例えば、ＦｅＮｉ不規則合金を窒化する窒化処理を行った後、窒化処理されたＦｅＮｉ不規則合金から窒素を除去する脱窒素処理を行うことにより、得られる。なお、不規則合金とは、原子の配列が規則性を持たずにランダムなものである。 Such L1 0 type FeNi ordered alloy, for example, after the nitriding process of nitriding the FeNi disordered alloy, by performing a denitrification treatment for removing nitrogen from nitriding treated FeNi disordered alloy, obtained It is done. An irregular alloy is an alloy in which the arrangement of atoms is random without regularity.
　本実施形態にかかるＬ１０型のＦｅＮｉ規則合金の製造方法について、図４に示される比較例Ｓ０～Ｓ１７および実施例Ｓ１８～Ｓ２４を参照して、具体的に説明する。 A method of manufacturing the L1 0 type FeNi ordered alloy according to the present embodiment, with reference to Comparative Examples S0 ~ S17 and Examples S18 ~ S24 shown in FIG. 4, specifically described.
　これら実施例および比較例は、熱プラズマ法、火炎噴霧法あるいは共沈法により作製されたＦｅＮｉ不規則合金の粉末試料を、図４に示される窒化処理条件、脱窒素処理条件で処理したものである。そして、これら処理後の合金について、Ｘ線回折測定を行い、Ｌ１０型規則構造が形成されているか否かを評価したものである。 In these examples and comparative examples, a powder sample of an FeNi disordered alloy produced by a thermal plasma method, a flame spray method, or a coprecipitation method is processed under the nitriding conditions and the denitrifying conditions shown in FIG. is there. Then, the alloy after these processes, subjected to X-ray diffraction measurement, is obtained by evaluating whether L1 0 ordered structure is formed.
　ここで、図４中に示される実施例および比較例のＦｅＮｉ不規則合金の粉末試料について、組成比はＦｅ：Ｎｉの原子量比であり、粒径は体積平均粒径（単位：ｎｍ）にて示してある。また、窒化処理条件および脱窒素処理条件については、処理温度（単位：℃）と処理時間（単位：ｈ）を示している。 Here, with respect to the FeNi disordered alloy powder samples of the example and comparative example shown in FIG. 4, the composition ratio is the atomic weight ratio of Fe: Ni, and the particle diameter is the volume average particle diameter (unit: nm). It is shown. Moreover, about the nitriding treatment condition and the denitrification treatment condition, the treatment temperature (unit: ° C.) and the treatment time (unit: h) are shown.
　窒化処理および脱窒素処理は、例えば図５に示される製造装置を用いて行われる。この製造装置は、ヒータ１１により加熱される加熱炉としての管状炉１０と、管状炉１０内に試料を設置するためのグローブボックス２０と、を備える。 Nitriding treatment and denitrification treatment are performed using, for example, a manufacturing apparatus shown in FIG. The manufacturing apparatus includes a tubular furnace 10 as a heating furnace heated by a heater 11 and a glove box 20 for installing a sample in the tubular furnace 10.
　また、図５に示されるように、この製造装置は、パージガスとしてのＡｒ（アルゴン）、窒化処理用のＮＨ３（アンモニア）、および、脱窒素処理用のＨ２（水素）を、切り替えて管状炉１０へ導入するガス導入部３０を備えている。 Further, as shown in FIG. 5, this manufacturing apparatus switches Ar (argon) as a purge gas, NH 3 (ammonia) for nitriding treatment, and H 2 (hydrogen) for denitrification treatment, and switches the tube. A gas introduction part 30 for introduction into the furnace 10 is provided.
　このような製造装置を用いた本実施形態の製造方法は次の通りである。まず、管状炉１０中にＦｅＮｉ不規則合金１００の粉末試料を設置しておく。窒化処理では、ＮＨ３ガスを管状炉１０に導入して管状炉１０内をＮＨ３雰囲気とし、所定温度で所定時間、ＦｅＮｉ不規則合金を加熱して窒化する。 The manufacturing method of this embodiment using such a manufacturing apparatus is as follows. First, a powder sample of the FeNi disordered alloy 100 is placed in the tubular furnace 10. In the nitriding treatment, NH 3 gas is introduced into the tubular furnace 10 to make the inside of the tubular furnace 10 an NH 3 atmosphere, and the FeNi disordered alloy is heated and nitrided at a predetermined temperature for a predetermined time.
　その後、脱窒素処理では、Ｈ２ガスを加熱炉に導入して管状炉１０内をＨ２雰囲気とし、所定温度で所定時間、窒化処理されたＦｅＮｉ不規則合金を加熱して窒素を除去する。こうして、材料全体の平均的な規則度Ｓが０．４以上で、かつ、保磁力Ｈｃが８７．５ｋＡ／ｍ以上であるＬ１０型のＦｅＮｉ規則合金が得られる。 Thereafter, in the denitrification treatment, H 2 gas is introduced into the heating furnace to make the inside of the tubular furnace 10 into an H 2 atmosphere, and the FeNi disordered alloy that has been nitrided at a predetermined temperature for a predetermined time is heated to remove nitrogen. Thus, in average degree of order S of the whole material is 0.4 or more, and, L1 0 type FeNi ordered alloy coercive force Hc is 87.5kA / m or more is obtained.
　なお、図４に示される実施例および比較例において、熱プラズマ法により作製されたＦｅＮｉ不規則合金の粉末試料は、日清エンジニアリング株式会社製の特注品であり、組成比Ｆｅ：Ｎｉ＝５０：５０、体積平均粒径：３０ｎｍ～１４０ｎｍのものである。 In the examples and comparative examples shown in FIG. 4, the FeNi disordered alloy powder sample produced by the thermal plasma method is a custom-made product manufactured by Nissin Engineering Co., Ltd., and the composition ratio Fe: Ni = 50: 50, volume average particle diameter: 30 nm to 140 nm.
　また、火炎噴霧法により作製されたＦｅＮｉ不規則合金の粉末試料は、シグマアルドリッチジャパン合同会社製の型番６７７４２６－５Ｇであり、組成比Ｆｅ：Ｎｉ＝５５：４５、体積平均粒径：５０ｎｍのものである。 Also, the FeNi disordered alloy powder sample produced by the flame spray method is model number 6774426-5G manufactured by Sigma-Aldrich Japan G.K., with a composition ratio of Fe: Ni = 55: 45 and volume average particle size: 50 nm. It is.
　また、共沈法により作製されたＦｅＮｉ不規則合金の粉末試料は、ＦｅＮｉ酸化物を水素還元したものであり、組成比Ｆｅ：Ｎｉ＝４７：５３、体積平均粒径：２００ｎｍのものである。 Further, the FeNi disordered alloy powder sample produced by the coprecipitation method is obtained by hydrogen reduction of FeNi oxide, and has a composition ratio of Fe: Ni = 47: 53 and a volume average particle size: 200 nm.
　図４に示されるように、比較例Ｓ０では、熱プラズマ法で作製された体積平均粒径：１０４ｎｍ、組成比Ｆｅ：Ｎｉ＝５０：５０のＦｅＮｉ不規則合金を、窒化処理も脱窒素処理も行わず、Ｘ線回折で評価した。 As shown in FIG. 4, in Comparative Example S0, a FeNi disordered alloy having a volume average particle size of 104 nm and a composition ratio of Fe: Ni = 50: 50 produced by a thermal plasma method is subjected to nitriding treatment and denitrifying treatment. No evaluation was performed by X-ray diffraction.
　比較例Ｓ１では、比較例Ｓ０と同じＦｅＮｉ不規則合金を用い、３００℃、４時間で窒化処理を行い、脱窒素処理は行わず、Ｘ線回折で評価した。比較例Ｓ２では、比較例Ｓ０と同じＦｅＮｉ不規則合金を用い、窒化処理は行わず、３００℃、４時間で脱窒素処理を行い、Ｘ線回折で評価した。 In Comparative Example S1, the same FeNi disordered alloy as in Comparative Example S0 was used, nitriding was performed at 300 ° C. for 4 hours, denitrification was not performed, and evaluation was performed by X-ray diffraction. In Comparative Example S2, the same FeNi disordered alloy as in Comparative Example S0 was used, nitriding was not performed, denitrification was performed at 300 ° C. for 4 hours, and evaluation was performed by X-ray diffraction.
　比較例Ｓ３では、比較例Ｓ０と同じＦｅＮｉ不規則合金を用い、３００℃、４時間で窒化処理を行い、３００℃、４時間で脱窒素処理を行い、Ｘ線回折で評価した。比較例Ｓ４では、火炎噴霧法で作製されたＦｅＮｉ不規則合金を用い、比較例Ｓ３と同様に窒化処理、脱窒素処理を行い、Ｘ線回折で評価した。比較例Ｓ５では、共沈法で作製されたＦｅＮｉ不規則合金を用い、比較例Ｓ３と同様に窒化処理、脱窒素処理を行い、Ｘ線回折で評価した。 In Comparative Example S3, the same FeNi disordered alloy as in Comparative Example S0 was used, subjected to nitriding treatment at 300 ° C. for 4 hours, denitrification treatment at 300 ° C. for 4 hours, and evaluated by X-ray diffraction. In Comparative Example S4, a FeNi disordered alloy produced by the flame spray method was used, and nitriding treatment and denitrogenating treatment were performed in the same manner as in Comparative Example S3, and evaluated by X-ray diffraction. In Comparative Example S5, a FeNi disordered alloy produced by a coprecipitation method was used, and nitriding treatment and denitrification treatment were performed in the same manner as in Comparative Example S3, and evaluation was performed by X-ray diffraction.
　比較例Ｓ６、Ｓ７、Ｓ８、Ｓ９は、窒化処理の処理温度を３２５℃、３５０℃、４００℃、５００℃と変えたこと以外は、比較例Ｓ３と同様に行われたものである。また、比較例Ｓ１０、Ｓ１１、Ｓ１２、Ｓ１３、Ｓ１４、Ｓ１５、Ｓ１６は、脱窒素処理の処理温度を１５０℃、２００℃、２５０℃、３５０℃、４００℃、４５０℃、５００℃と変えたこと以外は、比較例Ｓ３と同様に行われたものである。比較例Ｓ１７、実施例Ｓ１８、Ｓ１９、Ｓ２０、Ｓ２１、Ｓ２２、Ｓ２３、Ｓ２４は、体積平均粒径：３０ｎｍ～１４０ｎｍのものを用いて、窒化処理を温度３００℃、５０時間と長時間とし、脱窒素処理を３００℃、１時間としている。それ以外の条件は、比較例Ｓ３と同様としている。 Comparative Examples S6, S7, S8, and S9 were performed in the same manner as Comparative Example S3, except that the nitriding treatment temperature was changed to 325 ° C, 350 ° C, 400 ° C, and 500 ° C. Further, in Comparative Examples S10, S11, S12, S13, S14, S15, and S16, the denitrification treatment temperature was changed to 150 ° C., 200 ° C., 250 ° C., 350 ° C., 400 ° C., 450 ° C., and 500 ° C. Except for this, the same procedure as in Comparative Example S3 was performed. In Comparative Example S17, Examples S18, S19, S20, S21, S22, S23, and S24, those having a volume average particle diameter of 30 nm to 140 nm were used, and the nitriding treatment was performed at a temperature of 300 ° C. for 50 hours for a long time. Nitrogen treatment is performed at 300 ° C. for 1 hour. The other conditions are the same as in Comparative Example S3.
　Ｘ線回折によるＬ１０型規則構造の形成可否の評価は、図６に示される規則度Ｓが１である理想的なＦｅＮｉ規則合金のＸ線回折パターンとの比較により行える。Ｌ１０型のＦｅＮｉ規則合金では、図６中に示されるように、基本回折Ｐ２のピークに加えて、矢印で示される位置に超格子回折Ｐ１と呼ばれるピークが現れる。 Evaluation of formation whether L1 0 ordered structure by X-ray diffraction, the degree of order S shown in FIG. 6 can be performed by comparing the ideal FeNi ordered alloy X-ray diffraction pattern is 1. L1 In 0 type FeNi ordered alloy, as shown in FIG. 6, in addition to the peak of the fundamental diffraction P2, peak appears called superlattice diffraction P1 to the position indicated by the arrow.
　一方、図７に示されるように、ＦｅＮｉ不規則合金では、基本回折Ｐ２は現れるが、超格子回折Ｐ１は現れない。なお、これら図６、図７において、Ｘ線はＦｅのｋβ線（波長：１．７５６５３Å）を想定した。 On the other hand, as shown in FIG. 7, in the FeNi disordered alloy, the basic diffraction P2 appears, but the superlattice diffraction P1 does not appear. 6 and 7, the X-ray is assumed to be an Fe kβ ray (wavelength: 1.75653６５).
　このことから、上記した実施例および比較例においては、Ｘ線回折測定を行い、測定されたパターンにて超格子回折Ｐ１が現れれば、Ｌ１０型規則構造が形成されており、超格子回折Ｐ１が現れていなければ、Ｌ１０型規則構造が形成されていないと判断される。ここでは、超格子回折Ｐ１のなかでも、特にわかりやすい２８°と４０°のピークが明確に現れているかどうかにより、判断を行った。 Therefore, in the examples and comparative examples described above, subjected to X-ray diffraction measurement, if at measured pattern superlattice diffraction P1 icon that appears, L1 0 ordered structure is formed, a superlattice diffraction P1 If it does not appear, it is determined that the L1 0 type ordered structure is not formed. Here, the determination was made based on whether or not peaks of 28 ° and 40 ° that are particularly easy to understand clearly appear in the superlattice diffraction P1.
　これにより、図４では、Ｌ１０型規則構造が形成されているものは、「あり」とし、形成されていないものは、「なし」とした。図４に示されるように、「あり」は、比較例Ｓ３～Ｓ９、Ｓ１１～Ｓ１４、Ｓ１７、および、実施例Ｓ１８～Ｓ２４であり、「なし」は、比較例Ｓ０～Ｓ２、Ｓ１０、Ｓ１５、Ｓ１６であった。 Thus, in FIG. 4, it is intended to L1 0 ordered structure is formed, and that "there", which not formed, was evaluated as "None." As shown in FIG. 4, “present” is Comparative Examples S3 to S9, S11 to S14, S17, and Examples S18 to S24, and “None” is Comparative Examples S0 to S2, S10, S15, S16.
　また、上記した実施例および比較例のうち、Ｌ１０型規則構造が形成されているものについて、規則度Ｓの見積もりは、上記特許文献１に記載の方法に基づいて行った。この規則度Ｓの見積もりは、次の数式１に示されるＬ１０型のＦｅＮｉ規則合金における規則度Ｓの見積もり式により見積もることができる。 Further, among the examples and comparative examples described above, for those L1 0 ordered structure is formed, the estimate of the order parameter S, were based on the method described in Patent Document 1. Estimates of the order parameter S can be estimated by estimated expression rules of S in L1 0 type FeNi ordered alloy shown in Equation 1 below.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　ここで、数式１中、「Ｉｓｕｐ」は超格子回折Ｐ１のピークの積分強度であり、「Ｉｆｕｎｄ」は基本回折Ｐ２のピークの積分強度である。そして、「（Ｉｓｕｐ／Ｉｆｕｎｄ）ｏｂｓ」は、各実施例および比較例における測定されたＸ線回折パターンにおける超格子回折Ｐ１の積分強度と基本回折Ｐ２の積分強度との比である。また、「（Ｉｓｕｐ／Ｉｆｕｎｄ）ｃａｌ」は、図７のＸ線回折パターンにおける超格子回折Ｐ１の積分強度と基本回折Ｐ２の積分強度との比である。そして、数式１に示されるように、これら両比の平方根が規則度Ｓとして求められる。 In Equation 1, “I sup ” is the integrated intensity of the peak of the superlattice diffraction P1, and “I fund ” is the integrated intensity of the peak of the basic diffraction P2. “(I sup / I fund ) obs ” is a ratio between the integrated intensity of the superlattice diffraction P1 and the integrated intensity of the basic diffraction P2 in the X-ray diffraction patterns measured in the examples and comparative examples. “(I sup / I fund ) cal ” is a ratio between the integrated intensity of the superlattice diffraction P1 and the integrated intensity of the basic diffraction P2 in the X-ray diffraction pattern of FIG. Then, as shown in Equation 1, the square root of both ratios is obtained as the regularity S.
　各実施例および比較例について、測定されたＸ線回折パターンの典型例の一部が、図８，図９、図１０、図１１に示されている。このＸ線回折パターンに基づいてＬ１０型のＦｅＮｉ規則合金が得られているか否かについて説明すると共に、規則度Ｓや保磁力Ｈｃとの関係について説明する。 For each of the examples and comparative examples, some of typical examples of measured X-ray diffraction patterns are shown in FIGS. 8, 9, 10, and 11. FIG. Together it explained whether L1 0 type FeNi ordered alloy on the basis of the X-ray diffraction pattern is obtained, a description will be given of the relationship between the degree of order S and coercivity Hc.
　図８に示すように、窒化処理および脱窒素処理を共に行った比較例Ｓ３では、２８°と４０°の超格子回折Ｐ１のピークが明確に現れている。しかしながら、窒化処理および脱窒素処理を行っていない比較例Ｓ０や、窒化処理を行わずに脱窒素処理のみ行った比較例Ｓ２では、この超格子回折Ｐ１は現れなかった。なお、図８中、比較例Ｓ０の逆三角を記したピークは、酸化ＦｅＮｉであり、超格子回折Ｐ１ではない。これにより、窒化処理および脱窒素処理の両処理を行うことによって、Ｌ１０型のＦｅＮｉ規則合金が得られていることがわかる。 As shown in FIG. 8, in the comparative example S3 in which both the nitriding treatment and the denitrifying treatment are performed, the peaks of the superlattice diffraction P1 of 28 ° and 40 ° clearly appear. However, this superlattice diffraction P1 did not appear in Comparative Example S0 in which nitriding treatment and denitrification treatment were not performed and in Comparative Example S2 in which only nitriding treatment was performed without performing nitriding treatment. In FIG. 8, the peak marked with the inverted triangle in Comparative Example S0 is oxidized FeNi and not superlattice diffraction P1. Thus, by performing both the processing of nitriding treatment and denitrification treatment, it can be seen that the L1 0 type FeNi ordered alloy is obtained.
　また、図４に示すように、規則度Ｓについては、比較例Ｓ０、Ｓ２はＦｅＮｉ規則合金になっていないことから０であり、保磁力Ｈｃについては、それぞれ１０．２ｋＡ／ｍと４．０ｋＡ／ｍと小さい値であった。一方、比較例Ｓ３は、規則度Ｓが０．５２と比較的大きな値となったが、保磁力Ｈｃについては、３３．３ｋＡ／ｍと大きな値を得ることができなかった。 Further, as shown in FIG. 4, the degree of order S is 0 because Comparative Examples S0 and S2 are not FeNi ordered alloys, and the coercive force Hc is 10.2 kA / m and 4.0 kA, respectively. The value was as small as / m. On the other hand, in Comparative Example S3, the regularity S was a relatively large value of 0.52, but the coercive force Hc could not be as large as 33.3 kA / m.
　図９に示すように、窒化処理および脱窒素処理を共に行った比較例Ｓ３では、２８°と４０°の超格子回折Ｐ１のピークが明確に現れているが、窒化処理のみを行って脱窒素処理を行っていない比較例Ｓ１では、この超格子回折Ｐ１は現れなかった。図９中、比較例Ｓ１において黒丸を記したピークが、超格子回折Ｐ１とは異なる位置に現れているが、これは窒化ＦｅＮｉであり、超格子回折Ｐ１ではない。比較例Ｓ１は、窒化処理を行ったが脱窒素処理は行わないものであり、ＦｅＮｉの窒化物である。なお、図４に示すように、比較例Ｓ１については、ＦｅＮｉ規則合金になっていないことから規則度が０であり、保磁力Ｈｃも４．０ｋＡ／ｍと小さい値であった。 As shown in FIG. 9, in Comparative Example S3 in which both nitriding treatment and denitrification treatment were performed, peaks of superlattice diffraction P1 at 28 ° and 40 ° clearly appear. This superlattice diffraction P1 did not appear in Comparative Example S1 where no treatment was performed. In FIG. 9, the peak marked with a black circle in Comparative Example S1 appears at a position different from superlattice diffraction P1, but this is FeNi nitride, not superlattice diffraction P1. Comparative Example S1 is a nitride of FeNi that is subjected to nitriding treatment but not denitrifying treatment. As shown in FIG. 4, in Comparative Example S1, since the FeNi ordered alloy was not used, the degree of order was 0 and the coercive force Hc was a small value of 4.0 kA / m.
　図１０に示すように、比較例Ｓ３、Ｓ４、Ｓ５は、ＦｅＮｉ不規則合金の粉末試料の作製法および体積平均粒径が異なるもの同士であるが、いずれにおいても、２８°と４０°の超格子回折Ｐ１のピークが明確に現れている。なお、体積平均粒径の差異は、電子顕微鏡観察により容易に確認できる。このように、作製法および粒径が異なる試料においても窒化処理および脱窒素処理を行うことで、Ｌ１０型のＦｅＮｉ規則合金を製造できる。ただし、図４に示すように、比較例Ｓ４については、規則度Ｓが０．４１と比較的大きな値であるものの保磁力Ｈｃが２９．９ｋＡ／ｍと小さな値であった。また、比較例Ｓ５については、規則度Ｓが０．３７と小さな値で、保磁力Ｈｃも２７．６ｋＡ／ｍと小さな値であった。 As shown in FIG. 10, Comparative Examples S3, S4, and S5 are different from each other in the preparation method of the powder sample of FeNi disordered alloy and the volume average particle diameter, but in both cases, it exceeds 28 ° and 40 °. The peak of the grating diffraction P1 appears clearly. The difference in volume average particle diameter can be easily confirmed by observation with an electron microscope. In this way, by performing the nitriding treatment and denitrification treatment in a sample preparation method and the particle size is different, it can be produced L1 0 type FeNi ordered alloy. However, as shown in FIG. 4, in Comparative Example S4, the coercive force Hc was a small value of 29.9 kA / m, although the regularity S was a relatively large value of 0.41. Further, for Comparative Example S5, the degree of order S was as small as 0.37, and the coercive force Hc was as small as 27.6 kA / m.
　図１１に示すように、実施例Ｓ２１は、ＦｅＮｉ不規則合金の粉末試料の作製法については比較例Ｓ３とほぼ同様としつつ、窒化処理の時間を５０時間とし、脱窒素処理を１時間としたものである。実施例Ｓ２１では、２８°と４０°の超格子回折Ｐ１のピークが明確に現れている。また、体積平均粒径についても１４０ｎｍと比較的大きなものとされている。一方、図４に示すように、実施例Ｓ２１の規則度Ｓについては、０．６４と大きな値となっており、保磁力Ｈｃについても、１５０．６ｋＡ／ｍと大きな値を得ることができた。 As shown in FIG. 11, in Example S21, the method for preparing the FeNi disordered alloy powder sample was substantially the same as Comparative Example S3, the nitriding time was 50 hours, and the denitrification time was 1 hour. Is. In Example S21, peaks of the superlattice diffraction P1 at 28 ° and 40 ° clearly appear. The volume average particle diameter is also relatively large at 140 nm. On the other hand, as shown in FIG. 4, the regularity S of Example S21 is a large value of 0.64, and the coercive force Hc is a large value of 150.6 kA / m. .
　これらより、比較例Ｓ０～Ｓ２のように、窒化処理および脱窒素処理の少なくとも一方でも行わなかった場合には、Ｌ１０型のＦｅＮｉ規則合金を製造することができず、規則度Ｓも小さく、保磁力も小さな値となった。 From these, as in Comparative Examples S0 ~ S2, if not carried out in at least one of nitriding treatment and denitrification treatment is not able to produce L1 0 type FeNi ordered alloy, degree of order S is also small, The coercive force was also small.
　一方、比較例Ｓ３～Ｓ１７に示すように、窒化処理および脱窒素処理を行うことで、Ｌ１０型のＦｅＮｉ規則合金を製造することができる。しかしながら、窒化処理の時間が短い場合、ある程度の規則度Ｓを得ることができるようになるものの、保磁力Ｈｃについては十分な値を得ることができなかった。また、比較例Ｓ１０のように脱窒素処理の温度が低すぎたり、比較例Ｓ１５、Ｓ１６のように脱窒素処理の温度が高すぎる場合には、Ｌ１０型のＦｅＮｉ規則合金を製造することができず、規則度Ｓが０で、保磁力Ｈｃも小さな値となった。 On the other hand, as shown in Comparative Examples S3 ~ S17, by performing the nitriding treatment and denitrification treatment, it is possible to produce the L1 0 type FeNi ordered alloy. However, when the nitriding time is short, a certain degree of order S can be obtained, but a sufficient value cannot be obtained for the coercive force Hc. Also, too temperature of denitrification is low as in Comparative Example S10, when the temperature of the denitrification as in Comparative Example S15, S16 is too high, that the production of L1 0 type FeNi ordered alloy The degree of order S was 0 and the coercive force Hc was small.
　ここで、上記のＦｅＮｉ規則合金について、各種パラメータと規則度Ｓや保磁力Ｈｃとの関係について説明する。 Here, regarding the above-mentioned FeNi ordered alloy, the relationship between various parameters and the degree of order S and the coercive force Hc will be described.
　まず、規則度Ｓや保磁力Ｈｃと脱窒素処理条件もしくは窒化処理条件との関係、保磁力Ｈｃと体積平均粒径との関係、および、規則度Ｓと保磁力Ｈｃとの関係について、より詳細に述べる。 First, the relationship between the degree of order S and the coercive force Hc and the denitrification or nitriding conditions, the relationship between the coercive force Hc and the volume average particle diameter, and the relationship between the degree of order S and the coercive force Hc are more detailed. In the following.
　図１２は、脱窒素処理の処理温度以外は、同一の試料および窒化処理を行った比較例Ｓ６、Ｓ１０～Ｓ１６について、規則度Ｓと脱窒素処理の処理温度当該関係を表したものである。 FIG. 12 shows the relationship between the regularity S and the denitrification treatment temperature for the same sample and the comparative examples S6 and S10 to S16 subjected to the nitridation treatment except for the denitrification treatment temperature.
　まず、図１２に示される結果より、脱窒素処理の処理温度については、２５０℃以上４００℃以下が望ましいことが判る。図１２に示されるように、脱窒素処理の処理温度が２５０℃以上４００℃以下である比較例Ｓ１２、Ｓ６、Ｓ１３、Ｓ１４では、規則度Ｓが０．４以上であることが達成されていた。これらの例では、規則度Ｓがより大きな０．５以上となっていた。また、図１２中には示していないが、脱窒素処理の処理温度が２５０℃以上４００℃以下である比較例Ｓ１７や実施例Ｓ１８～Ｓ２４についても、規則度Ｓが０．４以上であった。しかし、当該処理温度が２５０℃未満である比較例Ｓ１０、Ｓ１１では、規則度Ｓは０．４未満であり、当該処理温度が４５０℃以上である比較例Ｓ１５、Ｓ１６では、処理温度が高すぎて超格子が分解していた。 First, from the results shown in FIG. 12, it is found that the treatment temperature for the denitrification treatment is preferably 250 ° C. or more and 400 ° C. or less. As shown in FIG. 12, in Comparative Examples S12, S6, S13, and S14 in which the treatment temperature of the denitrification treatment is 250 ° C. or more and 400 ° C. or less, the degree of order S was achieved to be 0.4 or more. . In these examples, the regularity S is 0.5 or more, which is larger. Further, although not shown in FIG. 12, the degree of order S was 0.4 or more in Comparative Example S17 and Examples S18 to S24 in which the treatment temperature of the denitrification treatment was 250 ° C. or more and 400 ° C. or less. . However, in Comparative Examples S10 and S11 where the processing temperature is less than 250 ° C., the regularity S is less than 0.4, and in Comparative Examples S15 and S16 where the processing temperature is 450 ° C. or more, the processing temperature is too high. The superlattice was disassembled.
　また、図４に示される結果より、脱窒素処理の時間については、１時間以下の短い時間でも良いことが判る。図４中の比較例Ｓ３、Ｓ４、Ｓ６～Ｓ９、Ｓ１２～Ｓ１４、Ｓ１７および実施例Ｓ１８～Ｓ２４に示されるように、４時間実施した場合であっても１時間実施した場合であっても所望の規則度Ｓを得ることができていた。また、図４中の実施例Ｓ１８～Ｓ２４に示されるように、脱窒素処理の時間が短くても、保磁力Ｈｃを８７．５ｋＡ／ｍ以上とすることができた。その反面、比較例Ｓ２～Ｓ１７に示すように、脱窒素処理の時間にかかわらず保磁力Ｈｃが８７．５ｋＡ／ｍ以上にならない場合もあった。これらのことから、規則度Ｓおよび保磁力Ｈｃの観点からは、脱窒素処理を行ってＦｅＮｉ規則合金を製造できていれば、脱窒素処理の時間については短くても良いということが確認された。 Further, from the results shown in FIG. 4, it can be seen that the denitrification treatment time may be as short as one hour or less. As shown in Comparative Examples S3, S4, S6 to S9, S12 to S14, S17 and Examples S18 to S24 in FIG. 4, it is desirable whether it is performed for 4 hours or 1 hour. The degree of regularity S can be obtained. Further, as shown in Examples S18 to S24 in FIG. 4, the coercive force Hc could be 87.5 kA / m or more even if the denitrification time was short. On the other hand, as shown in Comparative Examples S2 to S17, the coercive force Hc may not exceed 87.5 kA / m regardless of the time of denitrification. From these, it was confirmed that from the viewpoint of the degree of order S and the coercive force Hc, the time for the denitrification treatment may be short if the denitrification treatment can be performed to produce the FeNi ordered alloy. .
　一方、図４に示される結果より、窒化処理の処理温度については、３００℃以上５００℃以下が望ましいことが判る。図４の比較例Ｓ３～Ｓ９、Ｓ１１～Ｓ１４に示したように、窒化処理の処理温度を３００℃以上５００℃以下の範囲内とした場合、いずれの場合についても、ＦｅＮｉ規則合金が得られていた。このため、この温度範囲内であれば、ＦｅＮｉ規則合金を得ることができると言える。 On the other hand, the results shown in FIG. 4 indicate that the nitriding treatment temperature is preferably 300 ° C. or more and 500 ° C. or less. As shown in Comparative Examples S3 to S9 and S11 to S14 in FIG. 4, when the nitriding treatment temperature is in the range of 300 ° C. or more and 500 ° C. or less, the FeNi ordered alloy is obtained in any case. It was. For this reason, it can be said that an FeNi ordered alloy can be obtained within this temperature range.
　ただし、窒化処理の処理時間については、短いと十分ではないという結果が得られた。すなわち、図４の比較例Ｓ１２～Ｓ１４のように、窒化処理の処理温度を３２５℃とした場合に、処理時間を４時間としても、規則度Ｓは０．４以上になるものの、保磁力Ｈｃが８７．５ｋＡ／ｍ未満となった。これに対して、実施例Ｓ１８～Ｓ２４のように、窒化処理の処理温度を３００℃とした場合に、処理時間を５０時間とすると、規則度Ｓが０．４以上で、保磁力Ｈｃが８７．５ｋＡ／ｍ以上と大きく、磁性特性に優れたものとすることができた。このように、窒化処理の処理時間については高い保磁力Ｈｃを達成する上で重要な要素となっている。様々な実験を行った結果、処理時間を１０時間以上に設定すると、保磁力Ｈｃが８７．５ｋＡ／ｍ以上となった。この時間は、窒化処理の温度によって多少変化し、処理温度が高いほど若干処理時間を短くできるが、窒化処理の適正温度範囲として最も低い３００℃においては処理時間を１０時間以上にすることで、大きな保磁力Ｈｃを得ることができた。このため、３００℃より高い温度においては、処理時間を少なくとも１０時間以上にしていれば、保磁力Ｈｃを８７．５ｋＡ／ｍ以上にすることができる。 However, it was obtained that the nitriding treatment time was not sufficient if it was short. That is, as in the comparative examples S12 to S14 in FIG. 4, when the processing temperature of nitriding is 325 ° C., the order S is 0.4 or more even when the processing time is 4 hours, but the coercive force Hc Was less than 87.5 kA / m. On the other hand, as in Examples S18 to S24, when the processing temperature of nitriding is 300 ° C. and the processing time is 50 hours, the degree of order S is 0.4 or more and the coercive force Hc is 87. It was as large as 0.5 kA / m or more, and the magnetic properties were excellent. Thus, the nitriding treatment time is an important factor in achieving a high coercive force Hc. As a result of various experiments, when the treatment time was set to 10 hours or more, the coercive force Hc was 87.5 kA / m or more. This time slightly changes depending on the temperature of the nitriding treatment, and the processing time can be slightly shortened as the processing temperature is higher, but the processing time is set to 10 hours or more at 300 ° C. which is the lowest suitable temperature range for nitriding treatment. A large coercive force Hc could be obtained. For this reason, at a temperature higher than 300 ° C., the coercive force Hc can be 87.5 kA / m or more if the treatment time is at least 10 hours or more.
　なお、上記の図４に示した各例では、窒化処理の処理温度として、３００℃、３２５℃、３５０℃、４００℃、５００℃の例が挙げているが、勿論、窒化処理の処理温度は、これらの例に限定されるものではない。本実施形態の製造方法の場合には、窒化処理の温度を少なくとも３００℃以上５００℃以下の範囲としていれば良く、より広い温度範囲にもなり得る。 In each example shown in FIG. 4, examples of nitriding treatment temperatures are 300 ° C., 325 ° C., 350 ° C., 400 ° C., and 500 ° C. Of course, the nitriding treatment temperature is However, it is not limited to these examples. In the case of the manufacturing method of the present embodiment, the temperature of the nitriding treatment may be at least 300 ° C. or more and 500 ° C. or less, and may be a wider temperature range.
　さらに、保磁力Ｈｃについては、体積平均粒径にも影響を受けることが確認された。具体的には、体積平均粒径が大きいほど保磁力Ｈｃが大きくなる。図４に示すように、比較例Ｓ１７および実施例Ｓ１８～Ｓ２４に示すように、体積平均粒径が大きくなるに連れて保磁力Ｈｃが大きくなっている。比較例Ｓ１７のように体積平均粒径が３０ｎｍのときには、保磁力Ｈｃが５８．１ｋＡ／ｍと比較的大きな値になっていたものの、磁石材料や磁気記録材料としても用いることができる程の値ではなかった。しかしながら、実施例Ｓ１８～Ｓ２４のように、それぞれ体積平均粒径が４５ｎｍ、６０ｎｍ、８０ｎｍ、１２０ｎｍ、１４０ｎｍ、１３０ｎ、１００ｎｍのときには、保磁力Ｈｃがいずれも８７．５ｋＡ／ｍ以上となっていた。 Furthermore, it was confirmed that the coercive force Hc is also affected by the volume average particle diameter. Specifically, the coercive force Hc increases as the volume average particle size increases. As shown in FIG. 4, as shown in Comparative Example S17 and Examples S18 to S24, the coercive force Hc increases as the volume average particle size increases. When the volume average particle size is 30 nm as in Comparative Example S17, the coercive force Hc is 58.1 kA / m, which is a relatively large value, but it can be used as a magnet material or a magnetic recording material. It wasn't. However, as in Examples S18 to S24, when the volume average particle diameter was 45 nm, 60 nm, 80 nm, 120 nm, 140 nm, 130 n, and 100 nm, the coercive force Hc was 87.5 kA / m or more.
　このように、体積平均粒径を４５ｎｍ以上とすることで、規則度Ｓを０．４以上にできるだけでなく、保磁力Ｈｃについても８７．５ｋＡ／ｍ以上の大きな値を得ることが可能となる。なお、体積平均粒径については、基本的には大きくなるほど保磁力Ｈｃが大きくなるが、単磁区サイズを超える大きさとなるとその後保磁力Ｈｃが低下していく。例えば、２５０ｎｍを超えると保磁力Ｈｃが低下するものも発生している。このため、体積平均粒径が大き過ぎないようにすることが望ましい。体積平均粒径が２５０ｎｍを超えていても勿論構わないが、例えば体積平均粒径を６０ｎｍ以上かつ２５０ｎｍ以下にすれば、より確実に所望の保磁力Ｈｃを実現することができる。 Thus, by setting the volume average particle size to 45 nm or more, not only can the degree of order S be 0.4 or more, but also the coercive force Hc can be a large value of 87.5 kA / m or more. . As for the volume average particle diameter, basically, the larger the coercive force Hc, the larger the coercive force Hc. However, when the size exceeds the single magnetic domain size, the coercive force Hc decreases thereafter. For example, when the thickness exceeds 250 nm, some of the coercive force Hc is reduced. For this reason, it is desirable that the volume average particle diameter is not too large. Of course, the volume average particle diameter may exceed 250 nm, but for example, if the volume average particle diameter is 60 nm or more and 250 nm or less, the desired coercive force Hc can be realized more reliably.
　さらに、規則度Ｓと保磁力Ｈｃとについても、密接な関係がある。すなわち、規則度Ｓが大きくなるほど保磁力Ｈｃも大きくなる。そして、図１３に示したように、規則度Ｓが０．４以上になると保磁力Ｈｃが８７．５ｋＡ／ｍのものも製造可能になってくる。そして、規則度Ｓが０．６以上になると、より保磁力Ｈｃが８７．５ｋＡ／ｍ以上のものを製造できるようになる。勿論、図１３に示されるように、規則度Ｓが大きいだけでは所望の保磁力Ｈｃが得られないこともあるが、基本的には規則度Ｓが大きいほど保磁力Ｈｃを大きな値にすることが可能となる。特に、規則度Ｓが０．７以上になると、保磁力Ｈｃを９５．５ｋＡ／ｍ（１２００［Ｏｅ］）以上にすることが可能となる。 Furthermore, the degree of order S and the coercive force Hc are also closely related. That is, as the degree of order S increases, the coercive force Hc also increases. As shown in FIG. 13, when the regularity S is 0.4 or more, it is possible to manufacture a coercive force Hc of 87.5 kA / m. When the degree of order S is 0.6 or more, a product having a coercive force Hc of 87.5 kA / m or more can be manufactured. Of course, as shown in FIG. 13, the desired coercive force Hc may not be obtained if the regularity S is large, but basically the larger the regularity S, the larger the coercive force Hc. Is possible. In particular, when the degree of order S is 0.7 or more, the coercive force Hc can be 95.5 kA / m (1200 [Oe]) or more.
　以上説明したように、本実施形態では、規則度Ｓが０．４以上、かつ、保磁力Ｈｃが８７．５ｋＡ／ｍ以上のＦｅＮｉ規則合金としていることから、磁石材料や磁気記録材料としても用いることができる。特に、規則度Ｓが０．７以上、かつ、保磁力Ｈｃが９５．５ｋＡ／ｍのものとすることで、より保磁力Ｈｃが高く良好な磁石材料や磁気記録材料とすることが可能となる。例えば、このような高い規則度Ｓおよび保磁力Ｈｃを有するＬ１０型のＦｅＮｉ規則合金の粒子を磁粉として、この磁粉を押し固めて磁石形状にすることでＦｅＮｉ規則合金磁石を得ることができる。 As described above, in this embodiment, since the FeNi ordered alloy has a degree of order S of 0.4 or more and a coercive force Hc of 87.5 kA / m or more, it is also used as a magnet material or a magnetic recording material. be able to. In particular, when the degree of order S is 0.7 or more and the coercive force Hc is 95.5 kA / m, it is possible to obtain a good magnetic material or magnetic recording material having a higher coercive force Hc. . For example, particles of L1 0 type FeNi ordered alloy having such a high degree of order S and coercive force Hc as a magnetic powder, it is possible to obtain a FeNi ordered alloy magnet by the magnet shape compacted the magnetic particles.
　このように形成したＦｅＮｉ規則合金磁石は、例えば車両等に搭載されるモータ用の磁石として適用することができる。また、テープ状のフィルムに対してＦｅＮｉ規則合金の粒子を塗布すること等により、磁気記録媒体となる磁気テープを構成することもできる。本実施形態のようにして得たＦｅＮｉ規則合金については、高い保磁力Ｈｃを有していることから、磁気記録媒体の磁性体として用いたときに、環境磁場によって保存データが書き換えられることを抑制できる。 The FeNi ordered alloy magnet formed in this way can be applied as a magnet for a motor mounted on a vehicle, for example. In addition, a magnetic tape serving as a magnetic recording medium can be constituted by applying FeNi ordered alloy particles to a tape-like film. Since the FeNi ordered alloy obtained as in the present embodiment has a high coercive force Hc, when it is used as a magnetic body of a magnetic recording medium, it is suppressed that stored data is rewritten by an environmental magnetic field. it can.
　また、このようなＦｅＮｉ規則合金を得るには、ＦｅＮｉ不規則合金１００を窒化する窒化処理を行った後、窒化処理されたＦｅＮｉ不規則合金から窒素を除去する脱窒素処理を行えば良い。そして、窒化処理については、処理温度を３００℃以上５００℃以下、処理時間を１０時間以上とし、脱窒素処理については、処理温度を２５０℃以上４００℃以下とすれば良い。 In order to obtain such an FeNi ordered alloy, a nitriding treatment for nitriding the FeNi disordered alloy 100 may be performed, followed by a denitrification treatment for removing nitrogen from the nitridated FeNi disordered alloy. For the nitriding treatment, the treatment temperature is set to 300 ° C. to 500 ° C., the treatment time is set to 10 hours or more, and for the denitrification treatment, the treatment temperature is set to 250 ° C. to 400 ° C.
　また、Ｆｅの組成については５０原子％の近傍が、Ｌ１０型のＦｅＮｉ規則合金を形成しやすい組成である。そして、本実施形態では、上記の実施例および比較例に示されるように、組成範囲Ｆｅ：５５～４７原子％の合金において、規則度Ｓが０．４以上の高い規則化が実現されている。 Further, the vicinity of 50 atomic% for the composition of Fe, a composition tends to form an L1 0 type FeNi ordered alloy. In the present embodiment, as shown in the above-described examples and comparative examples, high ordering with an order S of 0.4 or more is realized in an alloy having a composition range of Fe: 55 to 47 atomic%. .
　また、ＦｅＮｉ不規則合金については、試料形状は特定しないが、窒化処理および脱窒素処理の短時間化のために、上述のように、粉末状試料であることが望ましい。特に、窒化処理に関しては時間を要することから、これらの処理を迅速に行うためには、ＦｅＮｉ不規則合金はナノ粒子試料であることが望ましい。そして、体積平均粒径を４５ｎｍ以上とすることで、より保磁力Ｈｃの高いＦｅＮｉ規則合金を得ることができる。 Further, although the sample shape of the FeNi disordered alloy is not specified, it is desirable to be a powder sample as described above in order to shorten the nitriding treatment and the denitrification treatment. In particular, since the nitriding process takes time, it is desirable that the FeNi disordered alloy is a nanoparticle sample in order to perform these processes quickly. And an FeNi ordered alloy with higher coercive force Hc can be obtained by setting the volume average particle size to 45 nm or more.
　また、本実施形態では、上述のように、作製法の異なるＦｅＮｉ不規則合金の粉末について規則化を確認している。さらに言えば、この不規則合金の作製方法は、上記した熱プラズマ法、火炎噴霧法、共沈法の各方法に限定されるものではない。なお、図４中には示していないが、不規則合金の作成方法として、熱プラズマ法以外の火炎噴霧法や共沈法の各方法で作成した不規則合金を用いて、窒化処理条件や脱窒素条件を実施例Ｓ１８～Ｓ２４の条件とした場合でも、これら各実施例と同様の結果が得られる。 Further, in this embodiment, as described above, the ordering of the powders of FeNi disordered alloys having different production methods is confirmed. Furthermore, the production method of the disordered alloy is not limited to the above-described thermal plasma method, flame spray method, and coprecipitation method. Although not shown in FIG. 4, as a method for producing an irregular alloy, nitriding treatment conditions and removal are performed using irregular alloys produced by flame spraying methods other than the thermal plasma method and coprecipitation methods. Even when the nitrogen conditions are the conditions of Examples S18 to S24, the same results as those of these Examples are obtained.
　また、Ｌ１０型のＦｅＮｉ規則合金を形成するためには、窒化処理された窒化物における窒素濃度は、Ｆｅ、Ｎｉおよび窒素の総量に対する原子量比として２０原子％から３３原子％程度が望ましい。 Also, L1 to form a 0 type FeNi ordered alloy, the nitrogen concentration in the nitride treated nitride, Fe, about 33 atomic% to 20 atomic% as atomic weight ratio to the total amount of Ni and nitrogen is preferable.
　また、窒化法、脱窒素法について限定するものではないが、本実施形態によれば、上記のように、アンモニアガスによる窒化、水素ガスによる脱窒素を行うことで不純物を混入させることなく、Ｌ１０型のＦｅＮｉ規則合金を得ることができる。 Further, although not limited to the nitridation method and the denitrification method, according to the present embodiment, as described above, L1 can be performed without mixing impurities by performing nitridation with ammonia gas and denitrification with hydrogen gas. A zero- type FeNi ordered alloy can be obtained.
　なお、上記実施例および比較例に代表されるように、ＦｅＮｉ不規則合金に窒化処理を行った後、窒素を除去する脱窒素処理を行うことにより、規則度Ｓが０．４以上で保磁力Ｈｃが８７．５ｋＡ／ｍ以上という高い値のＬ１０型のＦｅＮｉ規則合金にできる。これは、上記した従来のような分子線エピタキシーによる積層方法や、中性子照射しながら熱処理する方法に比べて、装置的にも工程的にも簡易な方法である。よって、本実施形態によれば、所望の規則度Ｓおよび保磁力Ｈｃを有するＬ１０型のＦｅＮｉ規則合金を、容易に合成することができる。 As represented by the above examples and comparative examples, after performing nitriding treatment on the FeNi disordered alloy, denitrification treatment for removing nitrogen is performed, so that the degree of order S is 0.4 or more and the coercive force. Hc can be the L1 0 type FeNi ordered alloy of high as or higher 87.5kA / m. This is a simple method both in terms of apparatus and process as compared with the conventional laminating method by molecular beam epitaxy and the method of heat treatment while irradiating with neutrons. Therefore, according to the present embodiment, the L1 0 type FeNi ordered alloy having a desired degree of order S and coercivity Hc, it can be easily synthesized.
　（第２実施形態）
　第２実施形態について説明する。本実施形態は、第１実施形態に対して更に規則度Ｓを高くできるようにするものである。本実施形態においても、基本的な製造工程については第１実施形態と同様であるため、第１実施形態と異なる部分についてのみ説明する。 (Second Embodiment)
A second embodiment will be described. In this embodiment, the regularity S can be further increased as compared with the first embodiment. Also in the present embodiment, the basic manufacturing process is the same as that of the first embodiment, and therefore only the parts different from the first embodiment will be described.
　本実施形態では、ＦｅＮｉ不規則合金からＬ１０型のＦｅＮｉ規則合金を形成する際に、中間生成物を生成することによって規則度Ｓを更に高くする。上記第１実施形態においても、窒化処理と脱窒素処理を行っているが、本実施形態では、窒化処理を終えたときに中間生成物としてＦｅＮｉＮが生成されるようにする。このとき、窒化処理によって的確に中間生成物が生成されるように、窒化処理に先立ち、ＦｅＮｉ不規則合金の表面に形成されている酸化膜の除去処理を行うようにしている。そして、中間生成物となるＦｅＮｉＮから脱窒素処理を行うことで、Ｌ１０型のＦｅＮｉ規則合金を形成する。 In the present embodiment, when forming the L1 0 type FeNi ordered alloy from FeNi disordered alloy, further increasing the degree of order S by generating an intermediate product. In the first embodiment as well, nitriding and denitrifying are performed, but in this embodiment, FeNiN is generated as an intermediate product when nitriding is completed. At this time, the oxide film formed on the surface of the FeNi disordered alloy is removed prior to the nitriding treatment so that the intermediate product is accurately generated by the nitriding treatment. By performing the denitrification process from FeNiN which is an intermediate product, to form an L1 0 type FeNi ordered alloy.
　具体的には、図１４に示すように、ＦｅＮｉ不規則合金を窒化処理を行い、図１に示したＩＩサイトに窒素を取り込むことでＩＩサイトにＮｉを多く含む中間生成物となるＦｅＮｉＮを形成する。そして、脱窒素処理を行い、ＩＩサイトから窒素を放出させることで、Ｌ１０型のＦｅＮｉ規則合金を構成する。 Specifically, as shown in FIG. 14, FeNi disordered alloy is subjected to nitriding treatment, and nitrogen is taken into the II site shown in FIG. 1 to form FeNiN as an intermediate product containing a large amount of Ni at the II site. To do. Then, a denitrification, by releasing nitrogen from II site, constituting the L1 0 type FeNi ordered alloy.
　まず、ＦｅＮｉ不規則合金を用意する。そして、ＦｅＮｉ不規則合金の表面に酸化膜が形成されていることから、窒化処理に先立ち、ＦｅＮｉ不規則合金の表面の酸化膜を除去する除去処理を行う。その後、除去処理に連続して窒化処理を行う。 First, an FeNi irregular alloy is prepared. Since the oxide film is formed on the surface of the FeNi disordered alloy, a removal process for removing the oxide film on the surface of the FeNi disordered alloy is performed prior to the nitriding process. Thereafter, a nitriding process is performed following the removal process.
　除去処理としては、酸化膜のエッチング雰囲気において、例えば３００℃～４５０℃の間での熱処理を行う。これにより、ＦｅＮｉ不規則合金の表面の酸化膜が除去され、窒化され易い表面状態となる。窒化処理としては、Ｎを含む雰囲気において、例えば２００℃～４００℃の間での熱処理を行う。これにより、酸化膜除去によって窒化され易くなったＦｅＮｉ不規則合金を的確に窒化することが可能となり、中間生成物となるＦｅＮｉＮが形成される。なお、ここでの窒化処理については、酸化膜を除去してから行っているため、より窒化反応し易くなっており、第１実施形態の場合よりも低温度であっても良くなる。このため、窒化処理の温度を２００℃～４００℃としているが、この温度を超えても良く、第１実施形態のように５００℃以下としていれば良い。 As the removal treatment, a heat treatment is performed at 300 ° C. to 450 ° C., for example, in an oxide film etching atmosphere. As a result, the oxide film on the surface of the FeNi disordered alloy is removed, and the surface state is easily nitrided. As the nitriding treatment, heat treatment is performed in an atmosphere containing N, for example, at 200 ° C. to 400 ° C. As a result, the FeNi disordered alloy that has been easily nitrided by removing the oxide film can be precisely nitrided, and FeNiN as an intermediate product is formed. Note that the nitriding treatment here is performed after removing the oxide film, so that the nitriding reaction is easier, and the temperature may be lower than in the case of the first embodiment. For this reason, the temperature of the nitriding treatment is set to 200 ° C. to 400 ° C., but this temperature may be exceeded, and it may be set to 500 ° C. or less as in the first embodiment.
　次に、中間生成物となるＦｅＮｉＮに対して脱窒素処理を行う。脱窒素処理としては、脱窒素雰囲気において、例えば２００～４００℃の間での熱処理を行う。これにより、中間生成物から窒素が脱離し、Ｌ１０型のＦｅＮｉ規則合金を形成することができる。このように、中間生成物となるＦｅＮｉＮを形成してから、Ｌ１０型のＦｅＮｉ規則合金を形成することで、より高い規則度Ｓを得ることが可能となる。 Next, denitrification treatment is performed on FeNiN as an intermediate product. As the denitrification treatment, heat treatment is performed at 200 to 400 ° C. in a denitrification atmosphere, for example. Thus, apart nitrogen from the intermediate product removed, it is possible to form an L1 0 type FeNi ordered alloy. Thus, after forming a FeNiN as the intermediate product, by forming the L1 0 type FeNi ordered alloy, it is possible to obtain a higher degree of order S.
　実際に、上記した除去処理、窒化処理および脱窒素処理を行い、Ｌ１０型のＦｅＮｉ規則合金を形成したときの具体例について説明する。 Indeed, the above-mentioned removal treatment is performed nitridation treatment and denitrification, a specific example of when forming an L1 0 type FeNi ordered alloy.
　まず、除去処理および窒化処理について、図１５Ａに示すプロファイルに従った処理を行った。 First, the removal process and the nitriding process were performed according to the profile shown in FIG. 15A.
　具体的には、上記した管状炉１０もしくはマッフル炉などの加熱炉を用意し、加熱炉内に平均粒径３０ｎｍのＦｅＮｉ不規則合金のナノ粒子試料を配置した。そして、加熱炉を室温から酸化膜の除去のための除去処理時の温度、ここでは４００℃まで昇温させた。このとき、加熱炉内に存在する酸素によってナノ粒子試料が酸化することを抑制するために、不活性ガスを導入しており、ここではＮ２（窒素）を導入しながら昇温工程を行った。 Specifically, a heating furnace such as the tubular furnace 10 or the muffle furnace described above was prepared, and a FeNi irregular alloy nanoparticle sample having an average particle diameter of 30 nm was placed in the heating furnace. Then, the heating furnace was heated from room temperature to a temperature at the time of removal treatment for removing the oxide film, here 400 ° C. At this time, in order to suppress the oxidation of the nanoparticle sample due to oxygen present in the heating furnace, an inert gas was introduced. Here, the temperature raising step was performed while introducing N 2 (nitrogen). .
　なお、不活性ガスとして、この後の窒化処理において利用することも可能なＮ２を用いたが、Ｎ２以外の不活性ガス、例えばＡｒ（アルゴン）やＨｅ（ヘリウム）等を用いるようにしても良い。 As the inert gas, N 2 that can be used in the subsequent nitriding treatment is used. However, an inert gas other than N 2 , such as Ar (argon) or He (helium), is used. Also good.
　そして、除去処理時の温度まで加熱炉を昇温させたら、Ｎ２の導入を停止して酸化膜のエッチングガスを導入することでエッチング雰囲気を生成し、所定時間加熱炉の温度を酸化膜の除去に必要な温度に維持した。本実験においては、エッチングガスとしてＨ２（水素）を用いており、１Ｌ／ｍｉｎのレートでＨ２を加熱炉内に導入し、加熱炉を１時間４００℃に維持した。これにより、ナノ粒子試料の表面の酸化膜を除去した。 Then, when the temperature of the heating furnace is raised to the temperature at the time of the removal process, the introduction of N 2 is stopped and the etching gas for the oxide film is introduced to generate an etching atmosphere. The temperature required for removal was maintained. In this experiment, is used with H 2 (hydrogen) as an etching gas, and H 2 introduced into the furnace at a rate of 1L / min, was maintained heated furnace 1 hour 400 ° C.. Thereby, the oxide film on the surface of the nanoparticle sample was removed.
　酸化膜の除去に必要な時間については任意であるが、例えば１０分以上の時間行うことで、酸化膜をある程度除去できることを確認している。また、酸化膜の除去の温度については、少なくとも３００℃～４５０℃の間であれば良い。 The time required for removing the oxide film is arbitrary, but it has been confirmed that the oxide film can be removed to some extent by performing, for example, a time of 10 minutes or more. The temperature for removing the oxide film may be at least between 300 ° C. and 450 ° C.
　酸化膜の除去の温度の下限値については、少なくとも３００℃以上であれば酸化膜を除去できることを確認していることから３００℃としている。ただし、３００℃未満であってもあっても、時間を掛ければ酸化膜の除去が行えると考えられる。また、酸化膜の除去の温度の上限値については、この後のＦｅＮｉ不規則合金の窒化が容易に行えるようにするために規定している。すなわち、酸化膜の除去の温度を４５０℃より高くすると、酸化膜が除去されたＦｅＮｉ不規則合金の表面が焼結し、窒化し難くなる。したがって、ＦｅＮｉ不規則合金の表面が焼結されることを抑制するために４５０℃以下としている。また、加熱炉内へのエッチングガスの導入レートについも任意であり、例えばＨ２の場合、少なくとも０．３～５Ｌ／ｍｉｎの範囲であれば酸化膜を除去できた。 The lower limit of the temperature for removing the oxide film is set to 300 ° C. because it has been confirmed that the oxide film can be removed if it is at least 300 ° C. or higher. However, even if it is less than 300 ° C., it is considered that the oxide film can be removed over time. Further, the upper limit value of the temperature for removing the oxide film is defined in order to facilitate the subsequent nitriding of the FeNi disordered alloy. That is, when the temperature for removing the oxide film is higher than 450 ° C., the surface of the FeNi disordered alloy from which the oxide film has been removed is sintered and is not easily nitrided. Accordingly, the temperature is set to 450 ° C. or lower in order to suppress the sintering of the FeNi disordered alloy surface. The rate of introduction of the etching gas into the heating furnace is also arbitrary. For example, in the case of H 2 , the oxide film can be removed if it is in the range of at least 0.3 to 5 L / min.
　このようにして、酸化膜の除去処理を終えた後、同じ加熱炉内において窒化処理を継続して行った。具体的には、加熱炉への導入ガスをエッチングガスから窒化ガスに切り替え、加熱炉内をＮが含まれる雰囲気とし、窒化に必要な温度を維持した。本実験においては、窒化ガスとしてＮＨ３（アンモニア）を用いており、５Ｌ／ｍｉｎのレートで加熱炉内に導入し、加熱炉を５０時間３００℃に維持した。これにより、ナノ粒子試料が窒化され、中間生成物となるＦｅＮｉＮが形成された。 Thus, after finishing the removal process of the oxide film, the nitriding process was continuously performed in the same heating furnace. Specifically, the gas introduced into the heating furnace was switched from the etching gas to the nitriding gas, the atmosphere inside the heating furnace was made to contain N, and the temperature necessary for nitriding was maintained. In this experiment, NH 3 (ammonia) was used as the nitriding gas, which was introduced into the heating furnace at a rate of 5 L / min, and the heating furnace was maintained at 300 ° C. for 50 hours. Thereby, the nanoparticle sample was nitrided, and FeNiN as an intermediate product was formed.
　窒化処理に必要な時間については任意であるが、例えば１０時間行うことで、中間生成物となるＦｅＮｉＮが合成できることを確認している。また、窒化処理の温度については、少なくとも２００℃～４００℃の間であれば良い。Ｎが含まれる雰囲気を生成するための加熱炉内への窒化ガスの導入レートについも任意であり、例えばＮＨ３の場合、少なくとも０．１～１０Ｌ／ｍｉｎの範囲であればナノ粒子試料を窒化できた。 Although the time required for the nitriding treatment is arbitrary, for example, it has been confirmed that FeNiN as an intermediate product can be synthesized by performing for 10 hours. The nitriding temperature may be at least between 200 ° C. and 400 ° C. The introduction rate of the nitriding gas into the heating furnace for generating the atmosphere containing N is also arbitrary. For example, in the case of NH 3 , the nanoparticle sample is nitrided at least in the range of 0.1 to 10 L / min. did it.
　このように、酸化膜の除去処理の後に引き続いて窒化処理を行った。このようにすることで、酸化膜を除去したＦｅＮｉ不規則合金の表面に再び酸化膜が形成されることを抑制できると共に、再び昇温工程を行わなくて済み、熱処理の簡素化および時間短縮化を図ることが可能となる。 Thus, the nitridation process was performed subsequently to the oxide film removal process. By doing so, it is possible to suppress the formation of an oxide film again on the surface of the FeNi disordered alloy from which the oxide film has been removed, and it is not necessary to perform the temperature raising process again, simplifying the heat treatment and shortening the time. Can be achieved.
　続いて、脱窒素処理を行った。脱窒素処理については、図１５Ｂに示すプロファイルに従った処理を行った。ここでは窒化処理後に時間を置いて脱窒素処理を行っているが、これらを連続して行うことも可能である。 Subsequently, denitrification was performed. About the denitrification process, the process according to the profile shown to FIG. 15B was performed. Here, denitrification is performed after a nitridation process, but it is also possible to perform these continuously.
　まず、上記した管状炉１０もしくはマッフル炉などの加熱炉を用意し、加熱炉内に図１５Ａのプロファイルに従って生成した中間生成物となるＦｅＮｉＮを配置した。そして、加熱炉を室温から脱窒素処理時の温度、ここでは３００℃まで昇温させた。このときも、加熱炉内に存在する酸素によって中間生成物であるＦｅＮｉＮが酸化することを抑制するために、不活性ガスを導入しており、ここではＮ２を導入しながら昇温工程を行った。 First, a heating furnace such as the tubular furnace 10 or the muffle furnace described above was prepared, and FeNiN as an intermediate product generated according to the profile of FIG. 15A was placed in the heating furnace. And the heating furnace was heated up from room temperature to the temperature at the time of a denitrification process, 300 degreeC here. In this case, in order to FeNiN an intermediate product by oxygen present in the heating furnace is prevented from being oxidized, and introducing an inert gas, subjected to heated process while introducing N 2 here It was.
　そして、脱窒素処理時の温度まで加熱炉を昇温させたら、Ｎ２の導入を停止して脱窒素処理を行うことができる雰囲気を生成し、所定時間加熱炉の温度を脱窒素に必要な温度に維持した。本実験においては、Ｈ２（水素）を用いて脱窒素を行うことができる雰囲気を生成しており、１Ｌ／ｍｉｎのレートでＨ２を加熱炉内に導入し、加熱炉を４時間３００℃に維持した。これにより、中間生成物であるＦｅＮｉＮから脱窒素を行った。 Then, when the heating furnace is heated up to the temperature at the time of denitrification treatment, an atmosphere in which introduction of N 2 is stopped and denitrification treatment can be performed is generated, and the temperature of the heating furnace is necessary for denitrification for a predetermined time. Maintained at temperature. In this experiment, an atmosphere in which denitrification can be performed using H 2 (hydrogen) is generated, H 2 is introduced into the heating furnace at a rate of 1 L / min, and the heating furnace is kept at 300 ° C. for 4 hours. Maintained. Thereby, denitrification was performed from FeNiN which is an intermediate product.
　脱窒素処理に必要な時間については任意であるが、例えば１時間以上行うことで、脱窒素処理によってＬ１０型のＦｅＮｉ規則合金を生成できることを確認している。また、脱窒素処理の温度については、少なくとも２００℃～４００℃の間であれば良いことを確認している。また、脱窒素処理が行える雰囲気を生成するための加熱炉内へのガスの導入レートについても任意であり、例えばＨ２の場合、少なくとも０．１～５Ｌ／ｍｉｎの範囲であれば脱窒素処理が行えた。 Optionally for the time required for the denitrification treatment, by performing for example 1 hour or more, it was confirmed that can generate L1 0 type FeNi ordered alloy by denitrification. Further, it has been confirmed that the temperature of the denitrification treatment may be at least between 200 ° C. and 400 ° C. Further, an arbitrary even the introduction rate of the gas into the heating furnace to generate an atmosphere denitrification can be performed, for example, in the case of H 2, denitrification treatment be in the range of at least 0.1 ~ 5L / min Was done.
　以上のような脱窒素処理を行うことで、Ｌ１０型のＦｅＮｉ規則合金を生成することができた。このように形成したＬ１０型のＦｅＮｉ規則合金について、材料全体の平均的な規則度Ｓを求めた。具体的には、粉末Ｘ線回折パターンにより、規則度Ｓを求めた。 By performing the denitrification treatment as described above, we were able to generate L1 0 type FeNi ordered alloy. This so-formed L1 0 type FeNi ordered alloy was determined an average order parameter S of the whole material. Specifically, the regularity S was determined from the powder X-ray diffraction pattern.
　例えば、規則度Ｓが１である場合におけるＬ１０型のＦｅＮｉ規則合金の粉末のＸ線回折パターンは、図１６のように表される。規則度Ｓは、Ｘ線回折パターンのうち、超格子反射である（００１）面からの回折ピーク、つまり超格子回折のピークの積分強度と、（１１１）面からの回折ピーク、つまり基本回折のピークの積分強度との比である回折強度比に対して図１７に示す関係を有している。このため、本実施形態のようにして生成したＬ１０型のＦｅＮｉ規則合金についても、Ｘ線回折パターンを求め、その結果から規則度Ｓを得ることができる。 For example, X-ray diffraction pattern of the powder of L1 0 type FeNi ordered alloy when the degree of order S is 1, is represented as shown in FIG. 16. The regularity S is the integrated intensity of the diffraction peak from the (001) plane that is the superlattice reflection, that is, the peak of the superlattice diffraction, and the diffraction peak from the (111) plane, that is, the fundamental diffraction of the X-ray diffraction pattern. FIG. 17 shows the relationship with the diffraction intensity ratio, which is the ratio with the integrated intensity of the peak. Therefore, for the FeNi ordered alloy on to the generated L1 0 type and as in this embodiment, obtaining the X-ray diffraction pattern, it is possible to obtain a degree of order S from the result.
　具体的に、本実施形態のように、ＦｅＮｉ不規則合金から酸化膜の除去処理を行ってから窒化処理を行って中間生成物であるＦｅＮｉＮを生成し、さらに脱窒素処理を行ってＬ１０型のＦｅＮｉ規則合金を生成したときのＸ線回折パターンを求めた。図１８は、その結果を示している。 Specifically, as in the present embodiment, FeNi irregular after performing removal processing of oxide film from the alloy subjected to nitriding treatment to generate a FeNiN an intermediate product, L1 0 type further performing denitrification X-ray diffraction pattern was obtained when an FeNi ordered alloy was produced. FIG. 18 shows the result.
　図１８に示されるように、（００１）面において超格子回折のピークが生じていることから、ＦｅＮｉ超格子ができていることが判る。この結果に基づいて、回折強度比を算出したところ、回折強度比が０．８であった。この回折強度比＝０．８のときの規則度Ｓを図１７から求めると、規則度Ｓが０．７１という高い値になった。 As shown in FIG. 18, since a peak of superlattice diffraction occurs in the (001) plane, it can be seen that a FeNi superlattice is formed. When the diffraction intensity ratio was calculated based on this result, the diffraction intensity ratio was 0.8. When the regularity S when the diffraction intensity ratio = 0.8 is obtained from FIG. 17, the regularity S is as high as 0.71.
　このように、本実施形態の製造方法によって生成したＬ１０型のＦｅＮｉ規則合金について、高い規則度Ｓを得ることができた。さらに、このＬ１０型のＦｅＮｉ規則合金について、磁気特性評価も行ったところ、異方性磁界として１１２０ｋＡ／ｍという比較的高い値を得ることができた。 Thus, the L1 0 type FeNi ordered alloy produced by the production method of the present embodiment, it was possible to obtain a high degree of order S. Furthermore, this L1 0 type FeNi ordered alloy, where also performed magnetic characterization, it was possible to obtain a relatively high value of 1120kA / m as anisotropy field.
　以上説明したように、本実施形態では、ＦｅＮｉ不規則合金に対して窒化処理を行って中間生成物であるＦｅＮｉＮを生成し、さらに脱窒素処理を行ってＬ１０型のＦｅＮｉ規則合金を生成している。このような製造方法により、全体の平均的な規則度Ｓが０．７以上という高い値となるＬ１０型のＦｅＮｉ規則合金を容易に生成することが可能となる。そして、このように高い規則度Ｓとすることで、ＦｅＮｉ規則合金の保磁力Ｈｃについても、高い値にすることが可能となる。したがって、より保磁力Ｈｃが８７．５ｋＡ／ｍ以上のＦｅＮｉ規則合金を得やすくすることが可能となる。 As described above, in the present embodiment, generates a FeNi an intermediate product by performing a nitriding process on disordered alloy Fenin, it generates an L1 0 type FeNi ordered alloy further subjected to denitrification ing. By such a manufacturing method, the average degree of order S of the whole it is possible to easily generate an L1 0 type FeNi ordered alloy as a high as 0.7 or more. And by setting it as this high degree of order S, it becomes possible also to make high value also about the coercive force Hc of a FeNi ordered alloy. Therefore, it is possible to easily obtain an FeNi ordered alloy having a coercive force Hc of 87.5 kA / m or more.
　特に、ＦｅＮｉ不規則合金の表面に形成されている酸化膜を除去するための除去処理を行ってから窒化処理を行うようにすることで、より的確に中間生成物を生成することが可能となる。したがって、除去処理を行うことで、より高い規則度Ｓを有するＬ１０型のＦｅＮｉ規則合金を得ることが可能となる。 In particular, an intermediate product can be generated more accurately by performing a nitriding process after performing a removing process for removing the oxide film formed on the surface of the FeNi disordered alloy. . Therefore, by performing the removal processing, it is possible to obtain L1 0 type FeNi ordered alloy having a higher degree of order S.
　なお、本実施形態では、酸化膜の除去を行うこと、窒化処理によって中間生成物を得ること、窒化処理の処理温度をより低温にできることについて、第１実施形態と異なることを示した。これ以外の事項、例えば脱窒素処理の時間や、体積平均粒径等については、第１実施形態と同様のことが言える。 In the present embodiment, it has been shown that the removal of the oxide film, the obtaining of an intermediate product by nitriding treatment, and the lowering of the nitriding treatment temperature can be made different from the first embodiment. Other matters, such as the time for denitrification, the volume average particle diameter, etc., can be said to be the same as in the first embodiment.
　（他の実施形態）
　本開示は、上記した実施形態に準拠して記述されたが、当該実施形態に限定されるものではなく、様々な変形例や均等範囲内の変形をも包含する。加えて、様々な組み合わせや形態、さらには、それらに一要素のみ、それ以上、あるいはそれ以下、を含む他の組み合わせや形態をも、本開示の範疇や思想範囲に入るものである。 (Other embodiments)
Although the present disclosure has been described based on the above-described embodiment, the present disclosure is not limited to the embodiment, and includes various modifications and modifications within an equivalent range. In addition, various combinations and forms, as well as other combinations and forms including only one element, more or less, are within the scope and spirit of the present disclosure.
　例えば、第１実施形態では窒化処理および脱窒素処理の条件の一例について説明した。しかしながら、ここで説明したのは各条件の一例を示したに過ぎない。すなわち、窒化処理および脱窒素処理によって、規則度Ｓが０．４以上、かつ、保磁力Ｈｃが８７．５ｋＡ／ｍ以上のＬ１０型のＦｅＮｉ規則合金を得ることができるならば、これら処理の処理温度、処理時間について、上記の例に限定するものではない。同様に、第２実施形態では、酸化膜の除去処理、窒化処理および脱窒素処理の条件の一例について説明したが、これらについても各条件の一例を示したに過ぎない。すなわち、規則度Ｓが０．４以上、かつ、保磁力Ｈｃが８７．５ｋＡ／ｍ以上のＬ１０型のＦｅＮｉ規則合金を得ることができるならば、これら処理の処理温度、処理時間について、上記の例に限定するものではない。 For example, in the first embodiment, an example of the conditions for nitriding and denitrifying has been described. However, what has been described here is merely an example of each condition. That is, the nitriding treatment and denitrification treatment, the degree of order S is 0.4 or more, and, if the coercive force Hc can be obtained FeNi ordered alloy of the above L1 0 type 87.5kA / m, these processes The processing temperature and processing time are not limited to the above example. Similarly, in the second embodiment, examples of the conditions for the oxide film removal process, the nitriding process, and the denitrifying process have been described. However, these are merely examples of the respective conditions. That is, the degree of order S is 0.4 or more, and, if it is possible to coercive force Hc obtain 87.5kA / m or more L1 0 type FeNi ordered alloy, processing temperatures of these processes, the processing time, the It is not limited to the example.
　また、上記第１、第２実施形態では、窒化処理および脱窒素処理を行うことによって、Ｌ１０型のＦｅＮｉ規則合金を得ているが、窒化処理および脱窒素処理以外の手法によってＬ１０型のＦｅＮｉ規則合金を得るようにしても良い。すなわち、ＦｅとＮｉとがＬ１０型のＦｅＮｉ規則構造と同じ格子構造で整列した化合物を合成する処理を行ったのち、この化合物からＦｅとＮｉ以外の不要な元素を除去する処理とを行うことでＬ１０型のＦｅＮｉ規則合金を得るようにしても良い。 Further, in the first and second embodiment, by performing the nitriding treatment and denitrification treatment, to obtain an L1 0 type FeNi ordered alloy, the L1 0 type by a method other than the nitriding treatment and denitrification An FeNi ordered alloy may be obtained. That is, after performing the process of the Fe and Ni to synthesize compounds that are aligned in the same lattice structure as the L1 0 type FeNi ordered structure, by performing a process of removing unnecessary elements other than Fe and Ni from the compound in may be obtained an L1 0 type FeNi ordered alloy.
　また、上記実施形態にかかるＬ１０型のＦｅＮｉ規則合金は、磁石材料および磁気記録材料等の磁性材料に適用されるが、このＦｅＮｉ規則合金の適用範囲は、磁性材料に限定されるものではない。 Also, L1 0 type FeNi ordered alloy according to the embodiment is applied to a magnetic material such as magnetic materials and magnetic recording materials, the scope of the FeNi ordered alloy is not limited to a magnetic material .

Claims (7)

  1. 　Ｌ１０型の規則構造を有し、材料の全体の平均的な規則度が０．４以上、かつ、保磁力が８７．５ｋＡ／ｍ以上であるＦｅＮｉ規則合金。 Having an L1 0 type ordered structure, overall average degree of order of the material is 0.4 or more, and, FeNi ordered alloy coercivity is 87.5kA / m or more.
  2. 　体積平均粒径が４５ｎｍ以上とされている請求項１に記載のＦｅＮｉ規則合金。 The FeNi ordered alloy according to claim 1, wherein the volume average particle diameter is 45 nm or more.
  3. 　前記規則度が０．７以上、かつ、前記保磁力が９７．５ｋＡ／ｍ以上である請求項１または２に記載のＦｅＮｉ規則合金。 The FeNi ordered alloy according to claim 1 or 2, wherein the degree of order is 0.7 or more and the coercive force is 97.5 kA / m or more.
  4. 　請求項１ないし３のいずれか１つに記載のＦｅＮｉ規則合金を含み構成されたＦｅＮｉ規則合金磁石。 An FeNi ordered alloy magnet comprising the FeNi ordered alloy according to any one of claims 1 to 3.
  5. 　Ｌ１０型の規則構造を有するＦｅＮｉ規則合金の製造方法であって、
    　ＦｅＮｉ不規則合金（１００）を窒化する窒化処理を行うことと、
    　前記窒化処理されたＦｅＮｉ不規則合金から窒素を除去する脱窒素処理を行うことにより、材料の全体の平均的な規則度が０．４以上、かつ、保磁力が８７．５ｋＡ／ｍ以上であるＬ１０型のＦｅＮｉ規則合金を得ることと、を含み、
    　前記窒化処理を行うことでは、前記窒化処理の処理温度を３００℃以上５００℃以下とし、処理時間を１０時間以上とするＦｅＮｉ規則合金の製造方法。     A method of manufacturing a FeNi ordered alloy having an L1 0 type ordered structure,
    Performing a nitriding treatment to nitride the FeNi disordered alloy (100);
    By performing a denitrification process for removing nitrogen from the nitridated FeNi disordered alloy, the overall average degree of order of the material is 0.4 or more and the coercive force is 87.5 kA / m or more. anda to obtain L1 0 type FeNi ordered alloy,
    By performing the nitriding treatment, a method of producing an FeNi ordered alloy in which a treatment temperature of the nitriding treatment is set to 300 ° C. or more and 500 ° C. or less and a treatment time is set to 10 hours or more.
  6. 　Ｌ１０型の規則構造を有するＦｅＮｉ規則合金の製造方法であって、
    　ＦｅとＮｉとがＬ１０型のＦｅＮｉ規則構造と同じ格子構造で整列した化合物を合成することと、
    　前記化合物からＦｅとＮｉ以外の不要な元素を除去することでＬ１０型のＦｅＮｉ規則合金を生成することと、を含み、
    　前記化合物を合成することでは、処理温度を２００℃以上５００℃以下とし、処理時間を１０時間以上として、ＦｅＮｉ不規則合金を窒化処理することで前記化合物として中間生成物となるＦｅＮｉＮを合成するＦｅＮｉ規則合金の製造方法。     A method of manufacturing a FeNi ordered alloy having an L1 0 type ordered structure,
    And the Fe and the Ni to synthesize compounds that are aligned in the same lattice structure as the L1 0 type FeNi ordered structure,
    Anda generating an L1 0 type FeNi ordered alloy by removing unnecessary elements other than Fe and Ni from the compound,
    By synthesizing the compound, FeNiN is synthesized as an intermediate product as the compound by nitriding the FeNi disordered alloy at a treatment temperature of 200 ° C. or more and 500 ° C. or less and a treatment time of 10 hours or more. Ordered alloy manufacturing method.
  7. 　ＦｅＮｉ不規則合金から酸化膜を除去することを含み、
    　前記化合物を合成することは、前記酸化膜を除去することの後に行われ、前記酸化膜が除去されたＦｅＮｉ不規則合金を窒化処理することで中間生成物となるＦｅＮｉＮを合成することである請求項６に記載のＦｅＮｉ規則合金の製造方法。     Removing the oxide film from the FeNi disordered alloy,
    The synthesis of the compound is performed after the oxide film is removed, and the FeNiN alloy as an intermediate product is synthesized by nitriding the FeNi disordered alloy from which the oxide film has been removed. Item 7. A method for producing an FeNi ordered alloy according to Item 6.
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